congenial, spent the remainder of his life there as a private teacher and industrial consultant. Not only was there an abundance of paid work in Manchester for private tutors because of a rising industrial middle class (Dalton’s most famous pupil was a brewer’s son, the physicist James Prescott Joule), but the presence of the Literary and Philosophical Society, whose Secretary Dalton became in 1800 and President from 1817 until his death, proved a congenial venue for the presentation and articulation of his scientific work. Dalton read his first scientific paper, on self-diagnosed colour blindness (long after known as Daltonism) to the Society in 1794. He went on reading papers and reports to the Society up to his death. From about 1815 onwards, however, Dalton failed more and more to keep pace with the chemical literature. In 1839 he suffered the ignominy of having a paper of his on phosphates and arsenates rejected by the Royal Society on the grounds that a superior account of these salts had already been published by Thomas Graham.
Despite such failings, Dalton retained the respect of the chemical and scientific communities. Together with two other Dissenters from Anglicanism, Michael Faraday and Robert Brown, the botanist, and despite the angry opposition of Oxford High Churchmen, Dalton was awarded an honorary degree by Oxford University in 1832. A year later the government awarded him a Civil List pension for life, and in 1834 Edinburgh University gave him another honorary degree. His final accolade was a public funeral in Manchester. Even if we grant that some of these honours served a secondary purpose of drawing attention to scientists and their contribution to culture in Victorian Britain, we are bound to ask: What did Dalton do to merit such public honours?
The straightforward answer is that Dalton rendered intelligible the many hundreds of quantitative analyses of substances that were recorded in the chemical literature and that he provided a model for the long-standing assumption made by chemists that compounds were formed from the combination of constant amounts of their constituents. He regarded chemical reactions as the reshuffling of atoms into new clusters (or molecules), these atoms and compound atoms being pictured in a homely way as little solid balls surrounded by a variable atmosphere of heat.
This statement, however, tells us little about Dalton’s originality; after all, the atomic theory of matter had existed for a good two-thousand years before Dalton’s birth. In Ireland, at the end of the eighteenth century, William Higgins (1762–1825) had used atomism in his A Comparative View of the Phlogiston and Antiphlogiston Theories (1789) to refute the phlogistic views of his countryman, Richard Kirwan. Higgins later claimed that Dalton had stolen his ideas – an inherently implausible notion that, nevertheless, has been supported by several historians in the past. In fact, Dalton’s originality lay in solving the problem of what philosophers of science have called transduction; he derived a way of calculating the relative weights of the ultimate particles of matter from observations and measurements that were feasible in the laboratory. Although atomic particles could never be individually weighed or seen or touched, Dalton provided a ‘calculus of chemical measurement’ that for the first time in history married the theory of atoms with tangible reality. He had transduced what had hitherto been a theoretical entity by building a bridge between experimental data and hypothetical atoms.
Dalton’s calculus involved four basic, but reasonable, assumptions. First, it was supposed that all matter was composed of solid and indivisible atoms. Unlike Newton’s and Priestley’s particles, Dalton’s atoms contained no inner spaces. They were completely incompressible. On the other hand, recognizing the plausibility of Lavoisier’s caloric model of changes of phase, Dalton supposed that atoms were surrounded by an atmosphere of heat, the quantity of which differed according to the solid, liquid or gaseous phase of the aggregate of atoms. A gas, for example, possessed a larger atmosphere of heat than the same matter in the solid state. Secondly, Dalton assumed, as generations of analysts before him had done, that substances (and hence their atoms) were indestructible and preserved their identities in all chemical reactions. If this law of conservation of mass and of the elements was not assumed, of course, transmutation would be possible and chemists would return to the dark days of alchemy. Thirdly, in view of Lavoisier’s operational definition of elements, Dalton assumed that there were as many different kinds of atoms as there were elements. Unlike Boyle and Newton, for Dalton there was not one primary, homogeneous ‘stuff’; rather, particles of hydrogen differed from particles of oxygen and all the particles that had so far been defined as elementary.
In these three assumptions Dalton moved away completely from the tradition of eighteenth-century matter theory, which had emphasized the identity of matter and of all material substances. In so doing. Dalton intimately bound his kind of atomism to the question of how elements were to be defined. In a final assumption, he proposed to do something that neither Lavoisier nor Higgins had thought of doing, namely to rid metaphysical atomism of its intangibleness by fixing a determinable property to it, that of relative atomic weight. To perform this transductive trick, Dalton had to make a number of simple assumptions about how atoms would combine to form compound atoms, the process he termed chemical synthesis. In the simplest possible case, ‘when only one combination of two bodies can be obtained, it must be presumed to be a binary one, unless some cause appear to the contrary’. In other words, although substances A and B might combine to form A2B2, it is simpler to assume that they will usually form just AB. Similarly, if ‘two combinations are observed, they must be presumed to be a binary and a ternary’:
A + 2B = AB2 or 2A + B = A2B
Dalton made similar rules for cases of three and four compounds of the same elements, and pointed out that the rules of synthesis also applied to the combination of compounds:
CD + DE = CD2E etc.
These assumptions of simplicity of composition, which, as we shall see, had a theoretical justification, have long since been replaced by different criteria. Although they led to many erroneous results, the assumptions proved fruitful since they allowed relative atomic weights to be calculated. Two examples, both given by Dalton, will suffice.
Hydrogen and oxygen were known to form water. Before 1815, when hydrogen peroxide was discovered, this was the only known compound of these two gases. Dalton quite properly assumed, therefore, that they formed a binary compound; in present-day symbols:
H + O = HO
From Humboldt and Gay-Lussac’s analyses of water, it was known that 87.4 parts by weight of oxygen combined with 12.6 parts of hydrogen to form water. This ratio, H : O :: 12.6 : 87.4, must also be the ratio of the individual weights of hydrogen and oxygen atoms that make up the binary atom of water. Since hydrogen is the lightest substance known, it made sense to’ adopt it as a standard and to compare all heavier chemical objects with it. If the hydrogen atom is defined as having a weight of 1, the relative atomic weight of an atom of oxygen will be roughly 7. (Dalton always rounded calculations up or down to the nearest whole number.) Similarly, Dalton assumed ammonia to be a binary compound of azote (nitrogen) and hydrogen. From Berthollet’s analysis he calculated the relative atomic weight of nitrogen to be 5 or, after further experiments in 1810, 6.
TABLE 4.1 Some of Dalton’s relative weights.
Dalton was well aware of the arbitrary nature of his rules of simplicity. In the second part of the New System in 1810 he allowed the possibility that water could be a ternary compound, in which case oxygen would be 14 times heavier than hydrogen; or, if two atoms of oxygen were combined with one of hydrogen, oxygen’s atomic weight would be 3.5. This uncertainty was to plague chemists for another fifty years.
