THE MODERN ATOMIC THEORY

EARLIEST  EMPIRICAL EVIDENCE

Near the end of the 18th century, two laws about chemical reactions emerged without referring to the notion of an atomic theory. The first was the law of conservation of mass, formulated by Antoine Lavoisier in 1789, which states that the total mass in a chemical reaction remains constant (that is, the reactants have the same mass as the products). The second was the law of definite proportions. First proven by the French chemist Joseph Louis Proust in 1799,^] this law states that if a compound is broken down into its constituent elements, then the masses of the constituents will always have the same proportions, regardless of the quantity or source of the original substance.

John Dalton studied and expanded upon this previous work and developed the law of multiple proportions: if two elements came together form more than one compound, then the ratios of the masses of the second element which combine with a fixed mass of the first element will be ratios of small integers. For instance, Proust had studied tin oxides and found that their masses were either 88.1% tin and 11.9% oxygen or 78.7% tin and 21.3% oxygen (these were tin(II) oxide and tin dioxide respectively). Dalton noted from these percentages that 100g of tin will combine either with 13.5g or 27g of oxygen; 13.5 and 27 form a ratio of 1:2. Dalton found an atomic theory of matter could elegantly explain this common pattern in chemistry - in the case of Proust's tin oxides, one tin atom will combine with either one or two oxygen atoms.

Dalton also believed atomic theory could explain why water absorbed different gases in different proportions: for example, he found that water absorbed carbon dioxide far better than it absorbed nitrogen. Dalton hypothesized this was due to the differences in mass and complexity of the gases' respective particles. Indeed, carbon dioxide molecules (CO₂) are heavier and larger than nitrogen molecules (N₂).

Dalton proposed that each chemical element is composed of atoms of a single, unique type, and though they cannot be altered or destroyed by chemical means, they can combine to form more complex structures (chemical compounds). This marked the first truly scientific theory of the atom, since Dalton reached his conclusions by experimentation and examination of the results in an empirical fashion.Various atoms and molecules as depicted in J

ohn Dalton's A NewSystemofChemical Philosophy (1808).

In 1803 Dalton orally presented his first list of relative atomic weights for a number of substances. This paper was published in 1805, but he did not discuss there exactly how he obtained these figures^. The method was first revealed in 1807 by his acquaintance Thomas Thomson, in the third edition of Thomson's textbook, A System of Chemistry. Finally, Dalton published a full account in his own textbook, A New System of Chemical Philosophy, 1808 and 1810.

Dalton estimated the atomic weights according to the mass ratios in which they combined, with hydrogen being the basic unit. However, Dalton did not conceive that with some elements atoms exist in molecules — e.g. pure oxygen exists as O₂. He also mistakenly believed that the simplest compound between any two elements is always one atom of each (so he thought water was HO, not H₂O). This, in addition to the crudity of his equipment, resulted in his table being highly flawed. For instance, he believed oxygen atoms were 5.5 times heavier than hydrogen atoms, because in water he measured 5.5 grams of oxygen for every 1 gram of hydrogen and believed the formula for water was HO (an oxygen atom is actually 16 times heavier than a hydrogen atom).

The flaw in Dalton's theory was corrected in 1811 by Amedeo Avogadro. Avogadro had proposed that equal volumes of any two gases, at equal temperature and pressure, contain equal numbers of molecules (in other words, the mass of a gas's particles does not affect its volume). Avogadro's law allowed him to deduce the diatomic nature of numerous gases by studying the volumes at which they reacted. For instance: since two liters of hydrogen will react with just one liter of oxygen to produce two liters of water vapor (at constant pressure and temperature), it meant a single oxygen molecule splits in two in order to form two particles of water. Thus, Avogadro was able to offer more accurate estimates of the atomic mass of oxygen and various other elements, and firmly established the distinction between molecules and atoms.

In 1827, the British botanist Robert Brown observed that dust particles inside pollen grains floating in water constantly jiggled about for no apparent reason. In 1905, Albert Einstein theorized that this Brownian motion was caused by the water molecules continuously knocking the grains about, and developed a hypothetical mathematical model to describe it. This model was validated experimentally in 1908 by French physicist Jean Perrin, thus providing additional validation for particle theory (and by extension atomic theory).