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Chalmers, Alan, "Atomism from the 17th to the 20th Century", The Stanford Encyclopedia of

Philosophy (Winter 2014 Edition), Edward N. Zalta (ed.):


<http://plato.stanford.edu/archives/win2014/entries/atomism-modern/>.

4. Chemical Atomism in the Nineteenth Century


4.1 Dalton's Atomism
Dalton was able to take for granted assumptions that had become central to chemistry since
the work of Lavoisier. Chemical compounds were understood as arising through the combination
of chemical elements, substances that cannot be broken down into something simpler by
chemical means. The weight of each element was understood to be preserved in chemical
reactions. By the time Dalton (1808) made his first contributions to chemistry the law of constant
composition of compounds could be added to this. [Joseph-Louis] Proust had done much to
substantiate experimentally the claim that the relative weights of elements making up a chemical
compound remain constant independent of its mode of preparation, its temperature and its state.
The key assumption of Dalton's chemical atomism is that chemical elements are composed of
ultimate particles or atoms. The least part of a chemical compound is assumed to be made up of
characteristic combinations of atoms of the component elements. Dalton called these compound
atoms. According to Dalton, all atoms of a given substance whether simple or compound, are
alike in shape, weight and any other particular. This much already entails the law of constant
proportions. Although Dalton himself resisted the move, Berzelius was able to show how
Dalton's theory can be conveniently portrayed by representing the composition of compounds in
terms of elements by chemical formulae in the way that has since become commonplace.
Hereafter this device is employed using modern conventions rather than any of the various ones
used by Berzelius and his contemporaries,
As Dalton stressed, once the chemical atomic theory is accepted, the promise is opened up of
determining the relative weights of atoms by measuring the relative weights of elements in
compounds. If an atom of element A combines with an atom of element B to form a compound
atom of compound AB, then the relative weights of A and B in the compound as measured in the
laboratory will be equal to the relative weights of atoms of A and B.
However, there is a serious under-determination of relative atomic weights by measurements of
combining weights in the laboratory. If the compound atom in our example were A2B rather
than AB then the relative atomic weight of B would be twice what it would be if the formula
were AB. Dalton himself attempted to resolve this problem with a simplicity assumption.
Formulae were always to take the simplest form compatible with the empirical data. If there was
only one compound of A and B known then it was assumed to be AB, whilst if there were two
then a more complicated compound, A2B or AB2 became necessary. As is illustrated by the latter
example, as well as the problem of the truth of the simplicity assumption there was the problem
of its ambiguity. Chemical atomists were to struggle for several decades with various solutions to
the problem of arriving at definitive formulae and relative atomic weights, as we shall see.

This deficiency of Dalton's atomism aside, links were forged between it and experimentally
determined combining weights that went beyond the law of constant proportions to include the
laws of multiple and reciprocal proportions. If two elements combine together in more than one
way to form compounds, as is the case with the various oxides of nitrogen and carbon, for
example, then Daltonian atomism predicts that the weights of one of the elements in each
compound, relative to a fixed weight of the second, will bear simple integral ratios to each other.
This is the law of multiple proportions, predicted by Dalton and soon confirmed by a range of
experiments. Daltonian atomism also predicts that if the weights of elements A and B that
combine with a fixed weight of element C are x and y respectively, then if A and B combine to
form a compound then the relative weights of A and B in the compound will be in the
ration x:y or some simple multiple of it. This law was also confirmed by experiment.
There is a further component that needs to be added to the content of early atomic chemistry,
although it did not originate with Dalton, who in fact did not fully embrace it. Gay Lussac
discovered experimentally that when gases combine chemically they do so in volumes that bear
an integral ratio to each other and to the volume of the resulting compound if gaseous, provided
that all volumes are estimated at the same temperature and pressure.
For instance, one volume of oxygen combines with two volumes of hydrogen to form two
volumes of steam. If one accepts atomism, this implies that there are some whole-number ratios
between the numbers per unit volume of atoms of various gaseous elements at the same
temperature. Following suggestions made by Avogadro and Ampere early in the second decade
of the nineteenth century, many chemists assumed that equal volumes of gases contain equal
numbers of atoms, with the important implication that relative weights of atoms could be
established by comparing vapour densities.
As Dalton clearly saw, this can only be maintained at the expense of admitting that atoms can
be split. The measured volumes involved in the formation of water, for example, entail that, if
equal volumes contain equal numbers of atoms then a water atom must contain half of an
oxygen atom. The resolution of these problems required a clear distinction between atoms of a
chemical substance and molecules of a gas, the grounds for which became available only later in
the century. This problem aside, the empirical fact that gases combine in volumes that are in
simple ratios to each other became a central component of chemistry, although it should be noted
that at the time Gay Lussac proposed his law, only a small number of gases were known to
chemists. The situation was to change with the development of organic chemistry in the next few
decades.

4.2 The Status of Daltonian Chemistry


If Dalton's atoms were regarded as ontologically basic, then there needed to be as many kinds
of matter as there are chemical elements. Further, atoms of each element needed to possess a
range of characteristic properties to account for chemical combination as well as physical
aggregation and other physical properties. As a philosophical theory of the ultimate nature of
material reality, Daltonian atomism was not a serious contender and was not treated as such. A

more significant issue is the status of Daltonian chemistry as an experimental science. To what
extent was Daltonian chemistry borne out by and able to fruitfully guide experiment?
A basic issue concerning the empirical statues of Daltonian atomism was already pinpointed in
an early exchange between Dalton (1814) and Berzelius (1815). Dalton was keen to present
himself as the Newton of chemistry. In his view, just as Newton had explained Keplers laws
with his new mechanics, so he, Dalton, had explained the laws of proportion with his atomism.
Without atomism the joint truth of the three laws of proportion is a mystery. Berzelius questioned
the experimental grounds for assuming anything stronger than the laws of proportion, since, he
argued, all of the chemistry could be accommodated by the latter. That is, nothing testable by the
chemistry of the time follows from Dalton's atomic theory that does not follow from the laws of
proportion plus the experimental law of combining volumes for gases.
Berzelius (1814) expressed his version of Daltonian chemistry using formulae. Dalton had
pictured atoms as spheres and compound atoms as characteristic arrangements of spheres.
Berzelius claimed that the two methods were equivalent but that his method was superior
because it was less hypotheticalHis point was that the testable empirical content of the two
theories were equivalent as far as the chemistry of the time was concerned, but that his version
was less speculative because it did not require a commitment to atoms. The symbols in Berzelian
formulae can be interpreted as representing combing weights or volumes without a commitment
to atoms.
A Daltonian atomist will typically take the hydrogen atom as a standard of weight and the atomic
weight of any other element will represent the weight of an atom of that element relative to the
weight of the hydrogen atom. On such an interpretation the formula H2O represents two atoms of
hydrogen combined with one of oxygen. But, more in keeping with the weight determinations
that are carried out in the laboratory, it is possible to interpret atomic weights and formulae in a
more empirical way. Any sample of hydrogen whatever can be taken as the standard, and the
atomic weight of a second element will be determined by the weight of that element which
combines with it. The formula H2O then represents the fact that water contains two atomic
weights of hydrogen for every one of oxygen. Of course, determining atomic weights and
formulae requires some decision to solve the under-determination problem, but that is the case
whether one commits to atoms or not.
Berzelius was right to point out that as far as being supported by and serving to guide the
chemistry of the time was concerned, his formulation using formulae served as well as Dalton's
formulation without committing to atomism. What follows from this will depend on one's stand
on confirmation and explanation in science. A strong-minded empiricist might conclude from
Berzeliuss observation that Dalton's atomism had no place in the chemistry of the time. Others
might agree with Dalton that the mere fact that Dalton's theory could explain the laws of
proportion in a way that no available rival theory could constituted a legitimate argument for it in
spite of the lack of evidence independent of combining weights and volumes. Atomism could be
defended on the grounds that attempts to articulate and improve it might well fruitfully guide
experiment in the future and lead to evidence for it that went beyond combining weights and

volumes. But such articulations would clearly require properties to be ascribed to atoms in
addition to their weight.
Berzelius himself took this latter option. He developed an atomic theory that attributed the
combination of atoms in compounds to electrostatic attractions. He developed a dualist theory
to bring order to compounds involving several types of molecules. For instance, he represented
copper sulphate as (CuO + SO3). Here electropositive copper combines with electronegative
oxygen but in a way that leaves the combination slightly electropositive, whereas electropositive
sulphur combines with oxygen in a way that leaves the combination slightly electronegative. The
residual charges of the radicals as they became known could then account for their combination
to form copper sulphate.
Berzelius's conjectures about the electrical nature of chemical combination owed their
plausibility to the phenomenon of electrolysis, and especially the laws governing it discovered by
Faraday, which linked the weights of chemicals deposited in electrolysis to chemical equivalents.
But evidence for the details of his atomistic theory independent of the evidence for the
experimental laws that the theory was designed to support was still lacking. Contemporaries of
Berzelius proposed other atomic theories to explain electrical properties of matter. Ampre
proposed electrical currents in atoms to explain magnetism and Poisson showed how electrostatic
induction could be explained by assuming atomic dipoles. In each of these cases some new
hypothesis was added to atomism for which there was no evidence independent of the
phenomenon explained

4.3 Progress in Organic Chemistry Using Chemical Formulae


The period from the third to the sixth decades of the nineteenth century witnessed spectacular
advances in the area of organic chemistry and it is uncontroversial to observe that these advances
were facilitated by the use of chemical formulae. Inorganic chemistry differs from organic
chemistry insofar as the former involves simple arrangements of a large number of elements
whereas organic chemistry involves complicated arrangements of just a few elements, mainly
carbon, hydrogen, oxygen and to a lesser extent, nitrogen.
It was soon to become apparent that the specification of the proportions of the elements in an
organic compound was not sufficient to identify it or to give an adequate reflection of its
properties. Progress became possible when the arrangements of the symbols representing the
elements in formulae were deployed to reflect chemical properties. The historical details of the
various ways in which chemical properties were represented by arrangements of symbols are
complex. (For details see Rocke (1984) and Klein (2003)). Here we abstract from those details to
illustrate the kinds of moves that were made.
The simplest formula representing the composition of acetic acid is CH2O using modern atomic
weights. This formula cannot accommodate the fact that, in the laboratory, the hydrogen in acetic
acid can be replaced by chlorine in four distinct ways yielding four distinct chemical compounds.
Three of those compounds are acids that have properties very similar to acetic acid, and in which
the relative weights of chlorine vary as 1:2:3. The fourth compound has the properties of a salt

rather than an acid. These experimental facts can be captured in a formula by doubling the
numbers and rearranging the symbols, so that we have C2H4O2, rearranged to read C2H3O2H. The
experimental facts can now readily be understood in terms of the substitution of one or more of
the hydrogens by chlorine, with the three chloro-acetic acids represented as C2H2ClO2,
C2HCl2O2H and C2Cl3O2H and the salt, acetyl chloride, as C2H3O2Cl. Such formulae came to be
known as rational formulae as distinct from the empirical formula CH2O. Representing the
replacement of one element in a compound by another in the laboratory by the replacement of
one symbol by another in a chemical formula became a standard and productive device that was
to eventually yield the concept of valency in the 1860s. (Oxygen has a valency of two because
two hydrogens need to be substituted for each oxygen.)
Other devices employed to fashion rational formulae involved the notion of a radical, a grouping
of elements that persisted through a range of chemical changes so that they play a role in organic
chemistry akin to that of elements in inorganic chemistry. Series of compounds could be
understood in terms of additions, for example to the methyl radical, CH3, or to the ethyl radical,
C2H5, and so on. Homologous series of compounds could be formed by repeatedly adding
CH2 to the formulae for such radicals so that the properties, and indeed the existence, of complex
compounds could be predicted by analogy with simpler ones. Another productive move involved
the increasing recognition that the action of acids needed to be understood in terms of the
replacement of hydrogen. Polybasic acids were recognised as producing two or more series of
salts depending on whether one, two or more hydrogens are replaced. Yet another important
move involved the demand that rational formulae capture certain asymmetric compounds, such
as methyl ethyl ether, CH3C2H5O, as distinct from methyl ether, (CH3)2O, and ethyl ether,
(C2H5)2O. By 1860, the idea of tetravalent carbon atoms that could combine together in chains
was added. By that stage, the demand that rational formulae reflect a wide range of chemical
properties had resulted in a set of formulae that was more or less unique. The underdetermination problem that had blocked the way to the establishment of unique formulae and
atomic weights had been solved by chemical means.

4.4 Implications of Organic Chemistry for Atomism


The previous section was deliberately written in a way that does not involve a commitment to
atomism. It is possible to understand the project of adapting rational formulae so that they
adequately reflect chemical properties by interpreting the symbols as representing combining
weights or volumes as Berzelius had already observed in his early debates with Dalton
A number of chemists involved in the early advances of organic chemistry who did adopt
atomism expressed their ontological commitment to chemical atoms. In doing so they
distinguished their theories from those brands of physical atomism that were in the tradition of
mechanical or Newtonian atomism and which sought to explain phenomena in general, and
chemistry in particular, by reference to a few physical properties of atoms. Chemical atoms had
more in common with natural minima insofar as they were presupposed to have properties
characteristic of the substances they were atoms of. Chemical atomism lent itself to the idea that

it was developments in chemistry that were to indicate which properties were to be attributed to
chemical atoms, as exemplified in the path that led to the property valency
Dalton's atomism had given a line on just one property of atoms, their relative weight. But it is
quite clear that they needed far richer properties to play [their] presumed role in chemistry. It was
to be developments in chemistry, and later physics, that were to give further clues about what
properties to ascribe to atoms. (We have seen how chemists came to ascribe the property of
valency to them.) There was no viable atomistic theory of chemistry in the nineteenth century
that was such that chemical properties could be deduced from it
The emergence of unique atomic weights and the structural formulae that organic chemistry had
yielded by the 1860s were to prove vital ingredients for the case for atomism that could
eventually be made. But there are reasons to be wary of the claim that atomism was responsible
for the rise of organic chemistry and the extent to which the achievement improved the case for
atomism needs to be elaborated with more caution that is typically the case
There is a case for claiming that correct atomic weights were the outcome of, rather than a
precondition for, progress in organic chemistry prior to 1860. After all, the majority of the
formulae productively involved in that dramatic progress were the wrong formulae from a
modern point of view! For instance, use of homologous series to project properties of lower
hydrocarbons on to higher ones are not affected if the number of carbon atoms in the correct
formulae are doubled, which results from taking 6 as the relative atomic weight of carbon, as
many of the contemporary organic chemists did.

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