Abstract
Electronegativity is a quantified, typical chemical concept, which correlates the ability of chemical species (atoms, molecules, ions, radicals, elements) to attract electrons during their contact with other species with measurable quantities such as dissociation energies, dipole moments, ionic radii, ionization potentials, electron affinities and spectroscopic data. It is applied to the description and explanation of chemical polarity, reaction mechanisms, other concepts such as acidity and oxidation, the estimation of types of chemical compounds and periodicity. Although this concept is very successful and widely used, and in spite of the fact that it is still subject to scientific investigations, neither a more than intuitive definition nor a generally accepted, logically clear and standardized quantification model has been developed. In the present work, electronegativity is presented and discussed with respect to its main conceptual and operational continuities and discontinuities. We try to analyze the epistemological status of electronegativity, conceived as a typical notion of chemical sciences. Under ‘epistemological status’ we subsume the issues of its reference, its historical persistence, and the relationship between its measurement and quantification.
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Notes
Jensen (2012) claims that the first qualitative description of electronegativity was due to the American physical chemist Worth H. Rodebush in 1925.
According to this set of rules, the electron shells have their own values of n1, the sum of which determines the shielding constant of the atoms n. Within this scale the value of n in Eq. 3 is 2, whereas in Gordy's scale the value is 1.
Eric Scerri has reacted to the scale of Allen and his argument about the reducibility of the periodic table to the Schrödinger's equation, and claims that "…the success of the periodic table does not rest on accepting a reductionist account of chemical phenomena and the structure of matter in terms of quantum mechanics and electronic configurations. I do not think I am alone in claiming that modern physics has not altered the periodic system in any fundamental way" (Scerri 1993, p. 5786).
Because his calculations referred to more-atomic substances, Malone had to assume bond angles, like the following: NH3/100°; PH3/98°; AsH3/96°; SbH3/94°.
Different bonding states of the same elemental kind, expressed as orbitals (s, p, sp, sp 2, sp 3) have different values of electronegativity. That means, for example, that the electronegativity of carbon atoms in diamond differs from that in graphite.
The situation with respect to the use of dipole moments as a starting point is slightly more complicated, as the work of Malone (1933) has shown. In order to obtain Δ-measures from dipole moments of hydrides, he had to assume molecule bond angles. The dipole moment is a resultant of the electrical impact of the constituents. There are heteropolar substances with a dipole moment of zero (e.g., CCl4), and homopolar substances with a dipole moment different from zero (e.g., O3).
Even hydrogen does not fit into group one of the periodic table with respect to its electronegativity values.
Note that, e.g., the ionization potentials do not follow a steady trend within the periods. There are small breaks between the s2-elements and the p1-elements, and between the p3-elements and the p4-elements, respectively. Thus, a linear and direct transformation of ionization potentials into electronegativity is not possible (see our discussion of the noble gases and Table 4).
Here we adopt the mainstream interpretation of “abstraction” by Hasok Chang, according to whom abstraction is “the act of removing certain properties from the description of an entity; the result is a conception that can correspond to actual entities but cannot be a full description of them.” (Chang 2004, p. 202). Abstraction, reduction, and modelling are related notions. Among them, modelling seems to be the most neutral, reduction has always an abstracting character, but abstraction must not at all purpose reduction.
We borrow the latter part of these attempts to characterize the central expressions from Heidelberger (1994). The author argues in favor of a correlative interpretation of the representational theory of measurement. That correlative interpretation has the advantage that any measurement depends on specific properties of certain representatives.
“It makes the language of construction, rather than of discovery, appropriate for experimentation as much as for theorizing” (van Fraassen 2008, p. 112).
The measurement of acidity has its own problems and peculiarities, cf. Chang (2012).
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Acknowledgements
This paper emerged from different efforts from both authors. On July 29 1999, K.R. presented the paper “On the Epistemological Status of Electronegativity” at the 3rd ISPC Summer Symposium in Columbia, South Carolina, United States. J.C.M. realized a research stay at Coburg, Germany, in the fall of 2014, during which the main material of the present paper was written. The following joint papers could be presented: “Inconsistency in quantum chemistry?” (ISPC, London, July 9 2014); “From substances to atoms: Electronegativity revisited” (PSA, Chicago, November 6 2014). The authors are grateful for all comments and criticism during all these presentations. Particular thanks go to Eric Scerri for his thoughtful comments and hints.
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Ruthenberg, K., González, J.C.M. Electronegativity and its multiple faces: persistence and measurement. Found Chem 19, 61–75 (2017). https://doi.org/10.1007/s10698-017-9278-3
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DOI: https://doi.org/10.1007/s10698-017-9278-3