Mole (unit) - History

History

The history of the mole is intertwined with that of molecular mass, atomic mass unit, Avogadro's number and related concepts.

The first table of atomic weights was published by John Dalton (1766–1844) in 1805, based on a system in which the atomic weight of hydrogen was defined as 1. These atomic weights were based on the stoichiometric proportions of chemical reactions and compounds, a fact that greatly aided their acceptance: It was not necessary for a chemist to subscribe to atomic theory (an unproven hypothesis at the time) to make practical use of the tables. This would lead to some confusion between atomic weights (promoted by proponents of atomic theory) and equivalent weights (promoted by its opponents and which sometimes differed from atomic weights by an integer factor), which would last throughout much of the nineteenth century.

Jöns Jacob Berzelius (1779–1848) was instrumental in the determination of atomic weights to ever-increasing accuracy. He was also the first chemist to use oxygen as the standard to which other weights were referred. Oxygen is a useful standard, as, unlike hydrogen, it forms compounds with most other elements, especially metals. However, he chose to fix the atomic weight of oxygen as 100, an innovation that did not catch on.

Charles Frédéric Gerhardt (1816–56), Henri Victor Regnault (1810–78) and Stanislao Cannizzaro (1826–1910) expanded on Berzelius' works, resolving many of the problems of unknown stoichiometry of compounds, and the use of atomic weights attracted a large consensus by the time of the Karlsruhe Congress (1860). The convention had reverted to defining the atomic weight of hydrogen as 1, although at the level of precision of measurements at that time — relative uncertainties of around 1% — this was numerically equivalent to the later standard of oxygen = 16. However the chemical convenience of having oxygen as the primary atomic weight standard became ever more evident with advances in analytical chemistry and the need for ever more accurate atomic weight determinations.

Developments in mass spectrometry led to the adoption of oxygen-16 as the standard substance, in lieu of natural oxygen. The current definition of the mole, based on carbon-12, was approved during the 1960s. The four different definitions were equivalent to within 1%.

Scale basis Scale basis
relative to 12C = 12
Relative deviation
from the 12C = 12 scale
Atomic weight of hydrogen = 1 1.00794(7) −0.788%
Atomic weight of oxygen = 16 15.9994(3) +0.00375%
Relative atomic mass of 16O = 16 15.9949146221(15) +0.0318%

The name mole is an 1897 translation of the German unit Mol, coined by the chemist Wilhelm Ostwald in 1894 from the German word Molekül (molecule). However, the related concept of equivalent mass had been in use at least a century earlier.

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