Why was unified atomic mass scale introduced and why was Oxygen - 16 replaced by carbon - 12 for standardizing atomic scale?


The mass scale has changed over time, largely due to different isotopes of the "baseline." Not surprisingly, there's a good Wikipedia article on the matter.

In the 20th century, until the 1960s chemists and physicists used two different atomic-mass scales. The chemists used a "atomic mass unit" (amu) scale such that the natural mixture of oxygen isotopes had an atomic mass 16, while the physicists assigned the same number 16 to only the atomic mass of the most common oxygen isotope (O-16, containing eight protons and eight neutrons). However, because oxygen-17 and oxygen-18 are also present in natural oxygen this led to two different tables of atomic mass. The unified scale based on carbon-12, $\ce{^12C}$, met the physicists' need to base the scale on a pure isotope, while being numerically close to the chemists' scale.

In short, Dalton suggested $\ce{^1H}$ as the basis of the mass scale, but Ostwald pushed later for $\ce{^16O}$. Unfortunately, no one knew about isotopes yet.

The problem was that physics stuck to isotopically pure O-16 for their mass scale, and chemistry used "oxygen" (i.e., with some O-17 and O-18 present). There's 0.028% difference between those scales. That may not sound like much, but with molecules of ~200-500 amu, it starts to add up.

Using C-12, it's isotopically pure (making physics happy) very close to the previous chemistry "O-16 + O-17 + O-18" scale.


In April 1957 at the bar in the Hotel Krasnapolski in Amsterdam, Nier suggested to Mattauch that the $\ce{^12C}$ = 12 mass scale be adopted because of carbon's use as a secondary standard in mass spectrometry. Also, $\ce{^12C}$ = 12 implied acceptable relative changes in the atomic weight scale, i.e., 42 parts-per-million (ppm) compared to 275 ppm for the $\ce{^16O}$ = 16 scale (which would not acceptable to chemists). Enthusiastically, Mattauch made a worldwide effort in the late 1950s to publicize the $\ce{^12C}$ = 12 scale and obtain the physicist's approval, while Wichers obtained the chemist's approval.

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    $\begingroup$ And since it was neither side's original choice it neatly sidesteps the whole "we won and you lost" issue. $\endgroup$ Jan 7 '15 at 17:53
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    $\begingroup$ Not sure what I'm misreading, but I don't get why carbon is more "isotopically pure" versus oxygen... C-13 is 1.1% versus O-18 at 0.2%. $\endgroup$
    – Nick T
    Jan 7 '15 at 20:05
  • $\begingroup$ Carbon per se isn't isotopically pure. The new standard is C-12, not "carbon." $\endgroup$ Jan 7 '15 at 21:52
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    $\begingroup$ Once isotopes were understood, the best compromise was to use isotopically pure C-12, since it minimized differences in masses, particularly in chemistry. $\endgroup$ Jan 7 '15 at 21:56
