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HO or H2O? How Chemists Learned to Count Atoms
Abstract
Water served as an emblematic locus for debates on the atomic constitution of matter. Today it is taken as common sense that water is H2O, but this was a highly disputed hypothesis for the first half-century of atomic chemistry. In Dalton’s original formulation of the atomic theory published in 1808 water was presented as HO, and consensus on the H2O formula (first proposed by Avogadro) was not reached until after the mid-century establishment of organic structural theory based on the concept of valency. The main epistemic difficulty was unobservability: molecular formulas could be ascertained only on the basis of the knowledge of atomic weights, and vice versa. There were multiple self-consistent sets of molecular formulas and atomic weights, which were employed in at least five different systems of atomic chemistry that flourished in the nineteenth century, each with its distinctive set of aims and methods and in productive mutual interaction. At the heart of the distinctive systems of atomic chemistry were different ways of operationalizing the concept of the atom (weighing, counting, and sorting atoms). It was operationalization that enabled atomic theories to become more than mere hypotheses that may or may not be consistent with observed phenomena. If we examine the crucial phase of development in which the consensus on H2O was achieved, the key was not the revival of Avogadro’s ideas by Cannizzaro, but the establishment of good atom-counting methods in substitution reactions. This, too, was a triumph of operationalization. We also need to keep in mind that the H2O consensus was not a straightforward unification of all systems of atomic chemistry; rather, it was a reconfiguration of the field which resulted in a new pluralistic phase of development.
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In 1868, The Times reported that poisons contained in dyes were affecting the public's health. A doctor informed a London magistrate that brilliantly coloured socks had caused severe "constitutional and local complaint" to several of his patients. In one case, a patient's foot had become so swollen that his boots had to be cut off. Respected chemist, William Crookes, offered to identify the poison if doctors would send him samples of the deadly socks. The story of how he solved the mystery gives this book its title and forms the basis of the first chapter. Written by a respected science historian and established author, this collection of essays contains 42 tales of chemists and their discoveries from the nineteenth and twentieth centuries. Other topics covered include: the quirky beliefs of American philanthropist, George Hodgkins; the development of the chemical laboratory since the 1830s, and the career of C.P. Snow before he became a novelist. Its broad coverage and modern approach makes it of interest to chemists, teachers, historians and laypeople with an interest in science. Written with a light style and presented in a series of unconnected vignettes the book is easy to dip into at leisure.
The renowned English chemist and meteorologist John Dalton (1766–1844) published A New System of Chemical Philosophy in two volumes, between 1808 and 1827. Dalton's discovery of the importance of the relative weight and structure of particles of a compound for explaining chemical reactions transformed atomic theory and laid the basis for much of what is modern chemistry. Volume 2 was published in 1827. It contains sections examining the weights and structures of two-element compounds in five different groups: metallic oxides; earthly, alkaline and metallic sulphurets; earthly, alkaline and metallic phosphurets; carburet; and metallic alloys. An appendix contains a selection of brief notes and tables, including a new table of the relative weights of atoms. A planned second part was never published. Dalton's work is a monument of nineteenth-century chemistry. It will continue to be read and enjoyed by anybody interested in the history and development of science.
This dissertation examines the development of synthetic organic chemistry in academic laboratories in nineteenth-century Germany. By studying the laboratory practice of chemists including Justus Liebig, August Hofmann and Albert Ladenburg, I show that early synthetical experiments were undertaken with primarily analytical goals, and that construction did not become the dominant purpose of organic synthesis until around 1880. I argue that successful constructive synthesis depended on a new glassware based practice whose unprecedented scale and intrinsic danger drove the construction of purpose-built chemical laboratories from the 1860s onwards. I therefore propose both a revised historiography of nineteenth-century organic chemistry, and a reinterpretation of the institutional revolution in late-nineteenth century physical sciences. I re-examine Liebig's motives for tackling the analysis of alkaloids, using his 1830 laboratory notebook to reconstruct Liebig's experimental approach to this technically demanding task, including his development of a new apparatus for the determination of carbon — the Kaliapparat. I show that incorporating analysis using the Kaliapparat into a reliable, pedagogically stable method involved the labour of the entire Giessen research school. Liebig, his students and assistants produced new chemical knowledge from indeterminate analytical data by a combination of theoretical and practical expertise acquired through disciplined laboratory training, and I argue that a similar philosophy of practice was equally essential in synthetic organic chemistry. Synthesis made chemical identity a focus of chemists' practical concern and I demonstrate that purity, transformation and identity were central to Hofmann's constitutional analysis and Ladenburg's eventual synthesis of the hemlock alkaloid coniine. I explore the origins of what I term the glassware revolution, and its role in resolving the question of chemical identity. Finally, I show how Ladenburg's synthesis depended on glass and glassblowing, and I argue that this new chemical practice both produced and depended on highly organised, specialised laboratory spaces.
Ernst Mach -- A Deeper Look has been written to reveal to English-speaking readers the recent revival of interest in Ernst Mach in Europe and Japan. The book is a storehouse of new information on Mach as a philosopher, historian, scientist and person, containing a number of biographical and philosophical manuscripts publihsed for the first time, along with correspondence and other matters published for the first time in English. The book also provides English translations of Mach's controversies with leading physicists and psychologists, such as Max Planck and Carl Stumpf, and offers basic evidence for resolving Mach's position on atomism and Einstein's theory of relativity.
Mach's scientific, philosophical and personal influence in a number of countries -- Austria, Germany, Bohemia and Yugoslavia among them -- has been carefully explored and many aspects detailed for the first time.
All of the articles are eminently readable, especially those written by Mach's sister. They are deeply researched, new interpretations abound, and the bibliography includes recent works by and about Mach from over a dozen countries.
The book also contains many articles by or about Mach's contemporaries, including Ostwald, Dingler, Weichert and, especially, Einstein. Finally, and most intriguingly, the original ideas of Japanese scholars are presented, built on Mach's philosophy. These demonstrate how Mach's world view is currently contributing to the solution of contemporary philosophical problems.
The development of chemical theory in the nineteenth century has been relatively little studied, compared with other sciences and other periods; much remains still to be explored. One notable example is chemical atomism, and its adjuncts such as valence and structure theory. Nonexistent at the beginning of the century, a generation or two later these ideas had moved to the very center of the science, which they still inhabit. The chemical atomic theory embodies outstanding examples of paper tools that provide not only explanatory and expository functions for what is already accepted as known, but also heuristic guidance in the further construction of a science. It may be of interest, therefore, to attempt an analysis of what some recent studies have revealed about this subject, along with indications of where further historical efforts may yield additional rewards.
Among the known forms of crystallized bodies, there is no one common to a greater number of substances than the regular octohedron, and no one in which a corresponding difficulty has occurred with regard to determining which modification of its form is to be considered as primitive; since in all these substances the tetrahedron appears to have equal claim to be received as the original from which all their other modifications are to be derived.
Preface 1. From pharmacy to chemistry 2. Organic analysis and the Giessen Research School 3. Liebig and organic chemistry, 1820-40 4. Liebig and the British 5. Liebig and commerce 6. Liebig and the farmers: agricultural chemistry 7. Liebig and the doctors: animal chemistry 8. Liebig on toast: the chemistry of food 9. Liebig and London: the chemistry of sewage 10. Populariser of science: chemical letters 11. Philosopher of science: the Bacon Affair 12. Death and assessment Appendices Bibliography Index.
http://www.upress.pitt.edu/BookDetails.aspx?bookId=35989
When the nature of any saline compound is proposed as the subject of inquiry to an analytic chemist, the questions that occur for his consideration are so varied and so numerous, that he will seldom be disposed to undertake a series of original experiments for the purpose of satisfying his inquiries, so long as he can rely upon the accuracy of those results that have been obtained by the labour of others, who have preceded him in this field of patient investigation. If, for instance, the salt under examination be the common blue vitriol, or crystallized sulphate of copper, the first obvious questions are, (1) How much sulphuric acid does it contain? (2) How much oxide of copper? (3) How much water? He may not be satisfied with these first steps in the analysis, but may desire to know further the quantities (4) of sulphur, (5) of copper, (6) of oxygen, (7) of hydrogen. As means of gaining this information, he naturally considers the quantities of various reagents that may be employed for discovering the quantity of sulphuric acid, (8) how much barytes, (9) carbonate of barytes, or (10) nitrate of barytes, would be requisite for this purpose; (11) How much lead is to be used in the form of (12) nitrate of lead; and when the precipitate of (13) sulphate of barytes or (14) sulphate of lead are obtained, it will be necessary that he should also know the proportion which either of them contains of dry sulphuric acid. He may also endeavour to ascertain the same point by means of (15) the quantity of pure potash, or (16) of carbonate of potash requisite for the precipitation of the copper. He might also use (17) zinc or (18) iron for the same purpose, and he may wish to know the quantities of (19) sulphate of zinc, or (20) sulphate of iron that will then remain in the solution.
And we must at all costs avoid over-simplification, which one might be tempted to call the occupational disease of philosophers if it were not their occupation.
(Austin 1965, p. 38).
Sometimes a theory is interpreted realistically—i.e., as literally true—whereas sometimes a theory is interpreted instrumentalistically—i.e., as merely a convenient device for summarizing, systematizing, deducing, etc., a given body of observable facts. This paper is part of a program aimed at determining the basis on which scientists decide on which of these interpretations to accept a theory. I proceed by examining one case: the nineteenth-century debates about the existence of atoms. I argue that there was a gradual transition from an instrumentalist to a realistic acceptance of the atomic theory, because of gradual increases in its predictive power, the “testedness” of its hypotheses, the “determinateness” of its quantities, and because of resolutions of doubts about the acceptability of its basic explanatory concepts.
Analytical table of contents Preface Introduction: rationality Part I. Representing: 1. What is scientific realism? 2. Building and causing 3. Positivism 4. Pragmatism 5. Incommensurability 6. Reference 7. Internal realism 8. A surrogate for truth Part II. Intervening: 9. Experiment 10. Observation 11. Microscopes 12. Speculation, calculation, models, approximations 13. The creation of phenomena 14. Measurement 15. Baconian topics 16. Experimentation and scientific realism Further reading Index.
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