Pauling Electronegativity

Linus Pauling described electronegativity as “the power of an atom in a molecule to attract electrons to itself.”¹ Basically, the electronegativity of an atom is a relative value of that atom's ability to attract election density toward itself when it bonds to another atom. The higher the electronegativity of an element, the more that atom will attempt to pull electrons towards itself and away from any atom it bonds to. The main properties of an atom dictate it's electronegativity are it's atomic number as well as its atomic radius. The trend for electronegativity is to increase as you move from left to right and bottom to top across the periodic table. This means that the most electronegative atom is Fluorine and the least electronegative is Francium.

There are a few different 'types' of electronegativity which differ only in their definitions and the system by which they assign values for electronegativity. For example, Mulliken electronegativity defines electronegativity as the "the average of the ionization energy and electron affinity of an atom."³ As we will see, this definition differs slightly from Pauling's definition of electronegativity.

Pauling Electronegativity

Linus Pauling was the original scientist to describe the phenomena of electronegativity. The best way to describe his method is to look at a hypothetical molecule that we will call XY. By comparing the measured X-Y bond energy with the theoretical X-Y bond energy (computed as the average of the X-X bond energy and the Y-Y bond energy), we can describe the relative affinities of these two atoms with respect to each other.

\[Δ\text{Bond Energies} = (X-Y)_{measured} – (X-Y)_{expected} \nonumber\]

If the electonegativities of X and Y are the same, then we would expect the measured bond energy to equal the theoretical (expected) bond energy and therefore the Δ bond energies would be zero. If the electronegativities of these atoms are not the same, we would see a polar molecule where one atom would start to pull electron density toward itself, causing it to become partially negative.

By doing some careful experiments and calculations, Pauling came up with a slightly more sophisticated equation for the relative electronegativities of two atoms in a molecule:

\[EN(X) - EN(Y) = 0.102 \sqrt{Δ}.\nonumber\]

In that equation, the factor 0.102 is simply a conversion factor between kJ and eV to keep the units consistent with bond energies.

By assigning a value of 4.0 to Fluorine (the most electronegative element), Pauling was able to set up relative values for all of the elements. This was when he first noticed the trend that the electronegativity of an atom was determined by it's position on the periodic table and that the electronegativity tended to increase as you moved left to right and bottom to top along the table. The range of values for Pauling's scale of electronegativity ranges from Fluorine (most electronegative = 4.0) to Francium (least electronegative = 0.7). ² Furthermore, if the electronegativity difference between two atoms is very large, then the bond type tends to be more ionic, however if the difference in electronegativity is small then it is a nonpolar covalent bond.

Exercise \(\PageIndex{1}\)

Explain the difference between Electronegativity and Electron Affinity

Exercise \(\PageIndex{2}\)

Predict the order or increasing electronegativity from the following elements

1. F, Li, C, O
2. Te, Cl, S, Se
3. Cs, At, Tl, I

References

1. Zumdahl, Steven S. "Chemical Principles" 5th Edition. Houghton Mifflin Company 2005. Chapter 13.2 "Electronegativity" pgs. 587-590.
2. Housecroft, Catherine E. et. al. "Inorganic Chemistry" 3rd Edition. Pearson Education Limited 2008. Chapter 2.5 "Electronegativity Values" pgs. 42-44
3. International Union of Pure and Applied Chemistry. "Electronegativity". goldbook.iupac.org/E01990.html.