What Chemists Do - Journal of Chemical Education (ACS Publications)

Jul 27, 2010 - What Chemists Do. John Olmsted III. Department of Chemistry and Biochemistry, California State University, Fullerton, Fullerton, Califo...
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Chemistry for Everyone

What Chemists Do John Olmsted III Department of Chemistry and Biochemistry, California State University, Fullerton, Fullerton, California 92834 [email protected]

The field of chemistry has mind-boggling breadth. To give just one measure, the American Chemical Society abstracting service, CAS, canvasses more than 10,000 scientific journals, from which it gleans nearly 700,000 document references yearly (1). The subject of chemistry is usually defined as the science of the composition, structure, properties, and reactions of matter, especially of atomic and molecular systems. However, this definition does not differentiate chemistry completely from other sciences, inasmuch as many physicists, geologists, and molecular biologists also study the structure and properties of matter. Given such breadth and overlap, students taking introductory chemistry courses are likely to be uncertain about what it is that chemists do. This uncertainty could be alleviated by an enumeration of the types of research undertaken by chemists. Surveying the annual output of this science would be an enormous task. Instead, this paper examines the chemical accomplishments that have been judged most admirable, as measured in the Nobel Prize awards in chemistry (2). A clear understanding of the essential features of chemistry would also be useful for those interested in the philosophy of science. It is paradoxical that, in spite of the immense scope of the field, chemistry has attracted little attention from philosophers of science. Schummer (3) has suggested that this may be in part because of the accepted wisdom, promulgated by physicists and not challenged by most chemists, that chemistry is reducible to physics. To the extent that such reduction is possible, a satisfactory philosophy of physics equally well applies to chemistry and there is no need for a separate philosophy of chemistry. But is chemistry indeed fully reducible to physics? To answer that question, philosophers need to have a good understanding of the types of activities that are valued by chemists. Analysis of the Nobel Prize in Chemistry Award Categories The Nobel Prize in Chemistry has been awarded annually since 1901, apart from 8 breaks during the period from 1916 to 1943: a total of 101 awards. What sorts of activities have been recognized in these awards? Analysis of the awards reveals that all the work can be assigned using just five categories of activities: synthesis, theorizing, exploration, description, and measurement. (A table listing the prizes and assignments is available in the supporting information.) The first activity in which chemists engage is synthesis, which is characteristic of chemistry. Synthesis is the creation of new substances or of known substances by new reaction pathways. The second Nobel Prize in Chemistry (1902) recognized Hermann Emil Fischer for “his work on sugar and purine syntheses” (2). Prizes for this type of accomplishment frequently went to chemists whose names are still associated with the types

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of synthesis that they pioneered: Fritz Haber (1918) was awarded the Nobel Prize “for the synthesis of ammonia from its elements” (2). Otto Diels and Kurt Alder (1950) shared the Nobel Prize “for their discovery and development of the diene synthesis” (2); Karl Ziegler and Giulio Natta (1963) were recognized “for their discoveries in the field of the chemistry and technology of high polymers” (2); and Robert Bruce Merrifield (1984) received the Nobel Prize “for his development of methodology for chemical synthesis on a solid matrix” (2). In common with scientists in other disciplines, chemists theorize about aspects of the discipline. Theorizing is the creation of a set of principles or laws that organize observations in a regular way. The very first Nobel Prize in Chemistry (1901) went to Jacobus van't Hoff for “discovery of the laws of chemical dynamics and osmotic pressure in solution” (2), and the third prize (1903) recognized Svante Arrhenius for “his electrolytic theory of dissociation” (2). Other clear examples of awards for theoretical advances include those to Paul J. Flory (1974) “for his fundamental achievements, both theoretical and experimental, in the physical chemistry of the macromolecules” (2); Ilya Prigogine (1977) “for his contributions to non-equilibrium thermodynamics, particularly the theory of dissipative structures” (2); Kenichi Fukui and Roald Hoffmann (1981) “for their theories, developed independently, concerning the course of chemical reactions” (2); and Walter Kohn and John Pople (1998) “for ...development of the density-functional theory and... of computational methods in quantum chemistry” (2). A third variety of research that has been extremely important in advancing chemical knowledge is exploration. Chemical exploration is speculative study of some domain of the subject that has not been previously known or has been neglected. The first Nobel Prize recognizing this type of work was the award in 1904, which went to William Ramsay for “the discovery of the inert gaseous elements in air, and his determination of their place in the periodic system” (2). Marie Curie, who was the first woman to win a Nobel Prize when she won the Nobel Prize in Physics (1903), became the first double recipient in 1911, when she was awarded the Nobel Prize in Chemistry for “the discovery of the elements radium and polonium” (2). The exploration of isotopes was frequently recognized, beginning with Francis Aston (1922) “for his discovery... of isotopes, in a large number of non-radioactive elements” (2); and Harold Urey (1934) “for his discovery of heavy hydrogen” (2). This variety of research continues to be recognized in recent years: Ahmed Zewail (1999) “for his studies of the transition states of chemical reactions using femtosecond spectroscopy” (2); Aaron Ciechanover, Avram Hershko, and Irwin Rose (2004) “for the discovery of ubiquitin-mediated protein degradation” (2); and Gerhard Ertl (2007) “for his studies of chemical processes on solid surfaces” (2).

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Detailed study of a domain that is not new but is incompletely characterized can be called description. Description is the systematic characterization of a phenomenon or substance, for example, the elucidation of structures. The first work of this type to be recognized by a Nobel Prize was that of Alfred Werner (1913), who was honored for “his work on the linkage of atoms in molecules by which he has thrown new light on earlier investigations and opened up new fields of research especially in inorganic chemistry” (2). Other prizewinners for this type of work are Richard Kuhn (1938), “for his work on carotenoids and vitamins” (2); Arne Tiselius (1948) “for his research on electrophoresis and adsorption analysis, especially for his discoveries concerning the complex nature of the serum proteins” (2); and Roger Kornberg (2006), “for his studies of the molecular basis of eukaryotic transcription” (2). A fifth variety of work recognized by Nobel Prizes in Chemistry is measurement. A broad definition of measurement includes purification as well as analysis. The first award for this type of endeavor went to Theodore Richards in 1914, “in recognition of his accurate determinations of the atomic weight of a large number of chemical elements” (2). Other examples are the awards to Fritz Pregl (1923) “for his invention of the method of micro-analysis of organic substances” (2); Jaroslav Heyrovsky (1959) “for discovery and development of the polarographic methods of analysis” (2); and Aaron Klug (1982) “for his development of crystallographic electron microscopy and his structural elucidation of biologically important nuclei acidprotein complexes” (2). As one might expect, not all of the Nobel-Prize-winning work can be assigned neatly to just one of these five types of activities. The 2008 Prize, for example, was awarded to Osamu Shimomura, Martin Chalfie, and Roger Tsien “for the discovery and development of the green fluorescent protein, GFP” (2). This work combined exploration (the discovery of the protein) and synthesis (development of ways to tag biological molecules). Of the 101 awards that have been made through 2009, 91 can be assigned to a single category; the other 10 involve work in a primary and a secondary category, giving a total of 111 assignments among the five types of activities. As Table 1 shows, there is a remarkably even distribution of awards among the five types. Table 1. Distribution of Nobel Prizes in Chemistry (1901-2009) among Activity Categories Category

Primary

Secondary

Percent of Total

Description

28

2

27

Exploration

20

3

21

Theorizing

20

3

21

Synthesis

19

2

19

Measurement

14

0

13

Additionally, all research chemists, and particularly those whose work is of Nobel Prize quality, typically work across more than one type of activity. New measurement techniques often are based on theoretical advances or the results of exploration. Willard Libby's 14C dating method (1960 prize), for example, was based on the theories of radioactive decay and of equilibration of elements in the biosphere, which in turn had been developed through extensive exploration. Exploration, in turn, may critically depend on advances in measurement. For example, Ramsay's discovery of the inert gases (1904 prize) depended on cryogenic techniques for achieving very low temperatures. Nearly half of the Nobel Prizes in chemistry honor the gathering of experimental information, either in virgin territory (exploration) or to characterize more fully already-known substances or phenomena (description). These are the types of activities that Ernest Rutherford probably would have dismissed as “stamp collecting”; yet, Rutherford himself was recognized in 1908 for “investigations into the disintegration of the elements”, an exploration. Indeed, nearly half the Nobel Prizes in Chemistry have recognized work of these types. One way of viewing any science is that it matures in three stages: determining the facts, classifying them in an orderly way, and determining the general laws that describe them (4). From this perspective, one might expect that, as a discipline matures, there will be fewer domains left to explore and describe, but more opportunities to express and refine theories. The temporal analysis of the Chemistry Nobel Prizes in Table 2 demonstrates otherwise (each quartile in Table 2 contains an equal number of prizes granted rather than an equal number of years, to take into account those years when no prize was awarded). The number of prizes recognizing these types of activities has remained remarkably constant for more than a century. This “steady state” distribution can be attributed to the opening up of new opportunities for research: as one subfield of chemistry matures and becomes amenable to theoretical treatment, new subfields are discovered, generating new opportunities for exploration and description. Comparison with the Nobel Prize in Physics Awards A similar analysis of the Nobel Prizes in Physics allows a comparison of the activities of research chemists with those of research physicists. Like chemists, physicists engage in theorizing, exploration, description, and measurement . Unsurprisingly, they do not do synthesis, which as earlier noted is an activity that is uniquely chemical. One might expect, however, that invention would play a comparable role for physicists. Some significant differences emerge from this analysis. Many Nobel Prizes in Physics recognize the development of unique apparatus, designed specifically to explore some theoretical prediction. The most striking example of this sort may be the 1984 award to Carlo Rubbia and Simon van der Meer, for

Table 2. Frequency of Awards in Chemistry with Time Quartile

Description

Exploration

Theorizing

Synthesis

Measurement

1901-1929

8

6

5

5

4

1930-1957

6

8

4

4

4

1958-1983

10

2

8

4

3

1984-2009

6

7

6

8

3

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Chemistry for Everyone Table 3. Distribution of Nobel Prizes in Physics (1901-2009) among Activity Categories Category

Primary

Secondary

Percent of Total

Theorizing

31

5

26

Exploration

20

11

22

Apparatus

26

3

21

Description

15

14

21

Invention

11

0

8

3

1

3

Measurement

achievements “leading to the successful operation of the CERN proton-antiproton collider” (5). In this instance, the machine itself is the accomplishment recognized with the award. In the few instances when Nobel Prizes in Chemistry have recognized the development of a new apparatus, that apparatus has widespread use in research: Heyrovsky's award (1959) for inventing and developing polaragraphy, and Ernst's award (1991) for highresolution NMR. In physics, design of an apparatus and its use to prove a specific aspect or prediction of theory are frequently jointly recognized in a Nobel Prize, leading to many more prizes being assigned to two varieties of activity rather than just one (31 dual activities in physics, 10 in chemistry). This reflects a different attitude toward apparatus among physicists and chemists, well illustrated by the following remark by physics Nobel Laureate Luis Alvarez (6): Most of us who become experimental physicists do so for two reasons; we love the tools of physics because to us they have intrinsic beauty, and we dream of finding new secrets of nature as important and as exciting as those uncovered by our scientific heroes. But we walk a narrow path with pitfalls on either side. If we spend all our time developing equipment, we risk the appellation of “plumber”, and if we merely use the tools developed by others, we risk the censure of our peers for being parasitic.

One would hardly describe chemistry prizewinners Ernst as a “plumber” or Zewail as a “parasite”. Further differences between the activities of physicists and chemists are revealed by the distribution of Nobel Prizes in Physics among categories, which appears in Table 3. (A table listing the prizes and assignments is available in the supporting information.) The most dramatic difference is the lesser importance of invention (synthesis) and measurement among physicists and the greater importance of theory. In similarity with chemistry, however, the Nobel Prizes in Physics have been divided nearly equally among four major categories. Like chemists, physicists carry out research in a variety of modes, each of which is valued by their peers. Three of the categories appearing in both tables, description, exploration, and theorizing, account for nearly 70% of the Nobel Prizes in both chemistry and physics, indicating that the fields have much in common. Moreover, the subdisciplines of physical chemistry and chemical physics suggest a continuous gradation between the fields rather than a sharp boundary. Yet, no Nobel Prize in Physics has ever been awarded to a scientist trained as a chemist. In contrast, nine persons trained as physicists have received awards in chemistry. These instances are worth examining. In 1908, Ernest Rutherford, whose training and academic appointments were in physics, was awarded the Nobel Prize for

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Chemistry, in recognition of “investigations into the disintegration of the elements, and the chemistry of radioactive substances” (2). President K. B. Hasselberg of the Swedish Royal Academy of Sciences explained this “crossover” in his prize presentation (7): Though Rutherford's work has been carried out by a physicist and with the aid of physical methods, its importance for chemical investigation is so far-reaching and self-evident, that the Royal Academy of Sciences has not hesitated to award to its progenitor the Nobel Prize designed for original work in the domain of chemistry—thus affording a new proof to be added to the numerous existing ones, of the intimate interplay one upon another of the various branches of natural science in modern times.

Clearly, the prize grantors felt that the subject that Rutherford studied, which was the chemical nature of nuclear radiation, characterized his accomplishments better than his background or the methods that he used. The 1911 Nobel Prize in Chemistry went to Marie Curie, who had shared the physics prize in 1903. Mme. Curie was trained as a physicist and was Professor of General Physics at the Sorbonne; yet the presentation speech for her Nobel Prize in Chemistry makes no mention of this. Perhaps the presenter felt that the citation was self-explanatory (8): [I]n recognition of her services to the advancement of chemistry by the discovery of the elements radium and polonium, by the isolation of radium and the study of the nature and compounds of this remarkable element[.]

Whereas the 1903 award in physics recognized the discovery and characterization of a physical phenomenon, spontaneous radioactivity, the citation for the 1911 award recognizes the discovery of two new elements, work that clearly lies within the domain of chemistry. The Nobel Prize in Chemistry for 1971 was awarded to Gerhard Herzberg. Like Rutherford, Herzberg's training and academic work were entirely in physics, and once again, the presenter, Sig Claesson of the Swedish Royal Academy of Sciences, found it appropriate to explain the “crossover” (9): One may now ask why Herzberg—originally a physicist and even famous as an astrophysicist—finally was awarded the Nobel Prize in Chemistry. The explanation is that around 1950 molecular spectroscopy had progressed so far that one could begin to study even complicated systems of great chemical interest. This is brilliantly demonstrated by Herzberg's pioneering investigations of free radicals. Knowledge of their properties is of fundamental importance to our understanding of how chemical reactions proceed.

As with Rutherford's work, the prize grantors focused on the subject area of Herzberg's work rather than his background or methods. Walter Kohn and John Pople shared the 1998 Nobel Prize in Chemistry. Kohn's entire career was in theoretical physics. Pople, in contrast, received his Ph.D. degree in mathematics but held positions in basic physics, chemical physics, and finally in chemistry. By his own admission, however, Pople was hardly trained as a chemist (10):

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I began my career in theoretical chemistry at the beginning of July [1948]. I had almost no chemical background, having last taken a chemistry course at BGS [Bristol Grammar School] at the age of fifteen.

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Once again, the award was made in chemistry because of the clear applications of the awardees' research in the field of chemistry, as indicated in press release announcing the prize (11): The Laureates have each made pioneering contributions in developing methods that can be used for theoretical studies of the properties of molecules and the chemical processes in which they are involved.

John Pople is not the only chemistry laureate whose career straddles the disciplines of chemistry and physics. The awardee in 1920 was Walther Nernst, who was recognized for work in thermochemistry. Nernst, trained as a physicist, worked extensively with physical chemists and was offered positions at German universities in physics before accepting one in physical chemistry at Gottingen (12). The 1936 prize went to Peter J. W. Debye, for confirming studies of molecular structure. Debye was a professor of physics in Berlin at the time of the award, but in 1940, he accepted a chemistry position at Cornell University. Two other physicists shared Nobel Prizes in Chemistry with chemist colleagues. The first was Edwin McMillan, who shared the 1951 prize with Glenn Seaborg. Both worked at the Lawrence Radiation Laboratory in Berkeley, but at different times. What they had in common was that both worked on the chemistry of the transuranium elements. In his acceptance speech, McMillan stated (13): “At this point I started to do some chemistry, and in spite of what the Nobel Committee may think, I am not a chemist.” The second was Alan Heeger, who shared the 2000 prize with two chemists, Alan MacDiarmid and Hidecki Shirakawa, for the discovery and characterization of conductive polymers. Their work, as described by all three of them in their Nobel autobiographies, was a genuine collaboration and cross-fertilization between chemists and a physicist (14). The eight chemistry prizes that were awarded to physicists covered work in all five categories of activities, but in most of these cases, a physicist probing the properties of matter discovered important features in the chemical domain. Consequently, the Nobel nominators and awards committees recognized the accomplishments as deserving of the chemistry prize. In other words, subject matter, rather than background or methods, defines where research is valued. Validity Inasmuch as the Nobel Prizes in Chemistry represent a very small and highly selective subset of the chemistry domain, it is important to analyze how accurately the sample matches the larger body of work in chemistry. There are at least three potential sources of inaccuracy. The criteria for the prizes may favor some types of research activity over others. The selection committee may be biased in favor of some types of activity. The assignments, being subjective, may not faithfully map what the prizewinners were doing. The following paragraphs address these possibilities. Alfred Nobel's will specified that this prize go to “the person who shall have made the most important chemical discovery or improvement” (15). The prize recognizes quality (importance) rather than quantity (total output). Nobel Prizes favor “breakthrough” research accomplishments, which are more likely to occur in frontier areas of the field. Consequently, although the categories reflect the types of work that chemists and physicists do, the percentages appearing in Tables 1 and 3 probably do not accurately reflect the numbers of working chemists and physicists engaged in each type of research activity. 1048

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The deliberations of the Nobel Prize committees are confidential, making assessment of how they reach their choices speculative. It is likely, however, that the personal prejudices of committee members played roles in at least some of the selections. Coffey (16) has described how personalities affected the awards during the years that Gilbert N. Lewis, perhaps the most talented chemist not to be awarded a Nobel Prize, was being considered. Dmitri Mendeleev did not receive a Nobel Prize, despite his development of the periodic table. Still, there have been very few contentious awards in chemistry, and controversy has tended to focus on who had priority rather than on the quality of the honored research (17). There have, in fact, been only a handful of controversial choices for the chemistry prize, indicating that the chemical community agrees with the choices. How accurate and unique are the assignments summarized in Table 1? They were based on examination of the presentation speeches and press releases announcing the awards, which highlight the key features of the work being honored. To reduce possible bias, a second category was assigned for those awards that appeared to recognize accomplishments of two varieties. Still, these assignments are perforce subjective. In addition, given the symbiosis among these several varieties of chemical endeavors, a critic might question the validity of the assignments made by any single author. Consequently, the percentages in Tables 1 and 3 should be viewed as approximate. Nevertheless, the overall conclusion does not depend on these percentages. Analysis of the awards of Nobel Prizes in Chemistry shows that chemists place high value on work in five different varieties of research endeavor: synthesis, theorizing, exploration, description, and measurement. Implications and Conclusions An analysis of the varieties of research activities that are recognized as valuable by Nobel Prizes shows that several types of research are equally highly valued. This suggests that chemists (and physicists) use several different, yet equally valid and useful, ways of approaching science; in other words, that instead of “the scientific method” there are several scientific methods. One way of teasing out how these methods differ is by analyzing the forms of questions that are essential to the different varieties of investigation. As Harwood has proposed in his activity model (18), questions are at the heart of scientific inquiry, and as was pointed out recently by Zare (19), “questions propel the world of inquiry and you should never underestimate the power of a simple question in organizing human endeavors”. Different sorts of questions drive the different varieties of research in chemistry and physics. • Description: What are the detailed properties of this substance or phenomenon? • Exploration: I wonder what lies beyond that horizon? • Theorizing: What fundamental laws or generalizations unify and explain this behavior? • Synthesis: How can I make this substance (or a substance that has these properties)? • Measurement: What is the correct value of this property, and what must be done to determine it? • Apparatus: What do I need to build in order to find the answer to this question? • Invention: How can I design something that will accomplish this task?

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Each type of question directs the researcher's attention along a different type of path. Each type of path is a valid scientific process, as indicated by the fact that Nobel Prizes in Chemistry and in Physics recognize outstanding accomplishments in all these directions. When we ask what chemists (and physicists) do, we must answer that they do a variety of things, each of which contributes to the advancement of science. The introduction to this paper included the question of the reducibility of chemistry to physics. The present analysis approaches this question from an operational perspective: what do chemists and physicists do that is highly valued? The conclusion is that chemists and physicists do and value activities that overlap in many respects but also differ significantly. From a philosophical perspective, however, chemistry and physics may also differ in more fundamental ways, either epistemological (how do physicists and chemists know what they know?) or ontological (what is the nature of physical and chemical reality?). Operational differences indicate that chemists and physicists approach the world using somewhat different tools, but these differences in approach do not, of themselves, indicate different views of the nature of scientific knowledge or the nature of reality. The most striking operational difference between chemistry and physics is the activity of synthesis, the creation of new substances and new reaction pathways to existing substances. While synthetic pathways cannot violate the laws of physics, neither do those laws appear to contain within them information needed to predict new substances or the mechanisms of new synthetic routes. As was pointed out by Rosenfeld and Bhushan (20), “chemical synthesis should be of interest to metaphysicians and philosophers of science”, particularly in regard to the reducibility of chemistry to physics.

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nobel_prizes/physics/laureates/1968/alvarez-speech.html (accessed Jun 2010). The Nobel Prize in Chemistry 1908 Presentation Speech by K. B. Hasselberg. http://nobelprize.org/nobel_prizes/chemistry/ laureates/1908/press.html (accessed Jun 2010). The Nobel Prize in Chemistry 1911, Marie Curie. http:// nobelprize.org/nobel_prizes/chemistry/laureates/1911/index.html (accessed Jun 2010). The Nobel Prize in Chemistry 1971 Presentation Speech by Stig Claesson. http://nobelprize.org/nobel_prizes/chemistry/laureates/ 1971/press.html (accessed Jun 2010). The Nobel Prize in Chemistry 1998, John A. Pople Autobiography. http://nobelprize.org/nobel_prizes/chemistry/laureates/1998/ pople-autobio.html (accessed Jun 2010). The Nobel Prize in Chemistry 1998, Press Release. http:// nobelprize.org/nobel_prizes/chemistry/laureates/1998/press.html (accessed Jun 2010). The Nobel Prize in Chemistry 1920, Biography of Walther Nernst. http://nobelprize.org/nobel_prizes/chemistry/laureates/1920/ nernst-bio.html (accessed Jun 2010). McMillan, E. The Transuranium Elements: Early History. In Nobel Lectures, Chemistry 1942-1962; Elsevier Publishing Company: Amsterdam, 1964; p 318. http://nobelprize.org/nobel_prizes/ chemistry/laureates/1951/mcmillan-lecture.html (accessed Jun 2010). The Nobel Prize in Chemistry 2000, Laureate Autobiographies. http://nobelprize.org/nobel_prizes/chemistry/laureates/2000/index. html (accessed Jun 2010). Nobelprize.org: Facts on the Nobel Prize in Chemistry. http:// nobelprize.org/nobel_prizes/chemistry/shortfacts.html (accessed Jun 2010). Coffey, P. Cathedrals of Science: The Personalities and Rivalries That Made Modern Chemistry; Oxford University Press: New York, 2008. Wikipedia Entry on Nobel Prize Controversies. http://en.wikipedia.org/wiki/Nobel_Prize_controversies (accessed Jun 2010). Harwood, W. S. A New Model for Inquiry: Is the Scientific Method Dead? J. Coll. Sci. Teach. 2004, 33, 29–33.Cf. Chem. Eng. News 2008, 86 (45), 4. Zare, R. N. The Power of the Question. Chem. Eng. News 2008, 86 (28), 3. Rosenfeld, S., Bhushan, N. Chemical Synthesis: Complexity, Similarity, Natural Kinds, and the Evolution of a “Logic. In Of Minds and Molecules: New Philosophical Perspectives on Chemistry, Rosenfeld, S., Bhushan, M., Eds.; Oxford University Press: New York, 2000; pp 187-207.

Supporting Information Available A spreadsheet listing the prizes and assignments is available via the Internet at http://pubs.acs.org.

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