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Well, I was doing research about the ways we can measure electronegativity and I just realized there must be an arbitrary electronegativity set for an specific element to give us the relative amounts of the other ones. Pauling used hydrogen and suggested 2.1 for its electronegativity which later was altered to 2.20. Now, the question is, why was the electronegativity of hydrogen suggested as 2.1 and why is it 2.20 right now? What are the secrets in those numbers?

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  • $\begingroup$ I might be wrong, but I remember my teacher saying that the Pauling scale was based on the arbitrary value of 4.0 for Florine, not 2.2 for Hydrogen. $\endgroup$ – Linuxios Dec 17 '14 at 19:26
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    $\begingroup$ Sorry to turn you down, but according to IUPAC, Wiki and many other reliable sources, H is the chosen element for the arbitrary electronegativity. However, in IUPAC gold book the value is documented as 2.1 as a sign of respect for Pauling's decision. $\endgroup$ – M.A.R. Dec 17 '14 at 19:49
  • $\begingroup$ No problem. That's good to know. $\endgroup$ – Linuxios Dec 17 '14 at 19:51
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Interestingly, the first paper from Pauling on electronegativity "The Nature of the Chemical Bond. IV. The Energy of Single Bonds and The Relative Electronegativity Of Atoms" published in 1932 gives a different scale with H = 0.0 and F = 2.0!

Later, he changed to 2.1 for H and 4.0 for F, e.g. http://scarc.library.oregonstate.edu/coll/pauling/bond/notes/sci5.001.14-notes-01.html

If we look through his book, on p. 90 we find the following text:

Following these there are given the values obtained by adding 2.05 to them...

The resulting numbers are then rounded to one decimal, from H = 2.05 to H = 2.1 and F = 4.0.

His notes are online (e.g., here) but there's no obvious explanation I can find yet.

My hunch is that he started with H = 0.0, and realized that the alkali metals would be negative numbers. The shifted scale gave Li ~ 1.0 and F ~ 4.0, which seem like "nice" numbers.

I tried to hunt down the reason for the move to 2.2 as the standard for hydrogen. The first reference seems to be by Huggins (J. Am. Chem. Soc., 1953, 75 (17), pp 4123–4126) but the paper itself doesn't really explain the reasoning.

Wikipedia suggests a paper by Allred, but that cites the Huggins paper for the 2.2 number.

Presumably more could be found with a very careful search through the papers of Pauling and Huggins, but I've never heard any clear explanations and the documents online don't give them either.

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