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| title | chunk | source | category | tags | date_saved | instance |
|---|---|---|---|---|---|---|
| Electronegativity | 3/4 | https://en.wikipedia.org/wiki/Electronegativity | reference | science, encyclopedia | 2026-05-05T10:52:24.353764+00:00 | kb-cron |
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{\displaystyle \chi ={n_{\rm {s}}\varepsilon _{\rm {s}}+n_{\rm {p}}\varepsilon _{\rm {p}} \over n_{\rm {s}}+n_{\rm {p}}}}
where εs,p are the one-electron energies of s- and p-electrons in the free atom and ns,p are the number of s- and p-electrons in the valence shell. The one-electron energies can be determined directly from spectroscopic data, and so electronegativities calculated by this method are sometimes referred to as spectroscopic electronegativities. The necessary data are available for almost all elements, and this method allows the estimation of electronegativities for elements that cannot be treated by the other methods, e.g. francium, which has an Allen electronegativity of 0.67. However, it is not clear what should be considered to be valence electrons for the d- and f-block elements, which leads to an ambiguity regarding their electronegativities calculated by the Allen method. On this scale, neon has the highest electronegativity of all elements, followed by fluorine, helium, and oxygen.
== Correlation of electronegativity with other properties ==
The wide variety of methods of calculation of electronegativities, which all give results that correlate well with one another, is one indication of the number of chemical properties that might be affected by electronegativity. The most obvious application of electronegativities is in the discussion of bond polarity, for which the concept was introduced by Pauling. In general, the greater the difference in electronegativity between two atoms the more polar the bond that will be formed between them, with the atom having the higher electronegativity being at the negative end of the dipole. Pauling proposed an equation to relate the "ionic character" of a bond to the difference in electronegativity of the two atoms, although this has fallen somewhat into disuse. Several correlations have been shown between infrared stretching frequencies of certain bonds and the electronegativities of the atoms involved: However, this is not surprising as such stretching frequencies depend in part on bond strength, which enters into the calculation of Pauling electronegativities. More convincing are the correlations between electronegativity and chemical shifts in NMR spectroscopy or isomer shifts in Mössbauer spectroscopy (see figure). Both these measurements depend on the s-electron density at the nucleus, and so is a good indication that the different measures of electronegativity describe "the ability of an atom in a molecule to attract electrons to itself".
== Trends in electronegativity ==
=== Periodic trends ===
In general, electronegativity increases on passing from left to right along a period and decreases on descending a group. Hence, fluorine is the most electronegative of the elements (not counting noble gases), whereas caesium is the least electronegative, at least of those elements for which substantial data is available. There are some exceptions to this general rule. Gallium and germanium have higher electronegativities than aluminium and silicon, respectively, because of the d-block contraction. Elements of the fourth period immediately after the first row of the transition metals have unusually small atomic radii because the 3d-electrons are not effective at shielding the increased nuclear charge, and smaller atomic size correlates with higher electronegativity (see Allred-Rochow electronegativity and Sanderson electronegativity above). The anomalously high electronegativity of lead, in particular, when compared to thallium and bismuth, is an artifact of electronegativity varying with oxidation state: its electronegativity conforms better to trends if it is quoted for the +2 state with a Pauling value of 1.87 instead of the +4 state.
=== Variation of electronegativity with oxidation number === In inorganic chemistry, it is common to consider a single value of electronegativity to be valid for most "normal" situations. While this approach has the advantage of simplicity, it is clear that the electronegativity of an element is not an invariable atomic property and, in particular, increases with the oxidation state of the element. Allred used the Pauling method to calculate separate electronegativities for different oxidation states of the handful of elements (including tin and lead) for which sufficient data were available. However, for most elements, there are not enough different covalent compounds for which bond dissociation energies are known to make this approach feasible.
The chemical effects of this increase in electronegativity can be seen both in the structures of oxides and halides and in the acidity of oxides and oxoacids. Hence CrO3 and Mn2O7 are acidic oxides with low melting points, while Cr2O3 is amphoteric and Mn2O3 is a completely basic oxide. The effect can also be seen in the dissociation constants pKa of the oxoacids of chlorine. The effect is much larger than could be explained by the negative charge being shared among a larger number of oxygen atoms, which would lead to a difference in pKa of log10(1⁄4) = −0.6 between hypochlorous acid and perchloric acid. As the oxidation state of the central chlorine atom increases, more electron density is drawn from the oxygen atoms onto the chlorine, diminishing the partial negative charge of individual oxygen atoms. At the same time, the positive partial charge on the hydrogen increases with a higher oxidation state. This explains the observed increased acidity with an increasing oxidation state in the oxoacids of chlorine.
=== Electronegativity and hybridization scheme === The electronegativity of an atom changes depending on the hybridization of the orbital employed in bonding. Electrons in s orbitals are held more tightly than electrons in p orbitals. Hence, a bond to an atom that employs an spx hybrid orbital for bonding will be more heavily polarized to that atom when the hybrid orbital has more s character. That is, when electronegativities are compared for different hybridization schemes of a given element, the order χ(sp3) < χ(sp2) < χ(sp) holds (the trend should apply to non-integer hybridization indices as well).