The 14th International Conference on

Miniaturized Systems for Chemistry and Life Sciences

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Electronegativity, symbol X, is a chemical property that describes the tendency of an atom to attract a shared pair of electrons (or electron density) towards itself. An atom's electronegativity is affected by both its atomic number and the distance at which its valence electrons reside from the charged nucleus. The higher the associated electronegativity number, the more an atom or a substituent group attracts electrons towards itself.

The term "electronegativity" was introduced by Jons Jacob Berzelius in 1811, though the concept was known even before that and was studied by many chemists including Avogadro. In spite of its long history, an accurate scale of electronegativity was not developed until 1932, when Linus Pauling proposed an electronegativity scale, which depends on bond energies, as a development of valence bond theory. It has been shown to correlate with a number of other chemical properties. Electronegativity cannot be directly measured and must be calculated from other atomic or molecular properties. Several methods of calculation have been proposed, and although there may be small differences in the numerical values of the electronegativity, all methods show the same periodic trends between elements.

As it is usually calculated, electronegativity is not a property of an atom alone, but rather a property of an atom in a molecule. Properties of a free atom include ionization energy and electron affinity. It is to be expected that the electronegativity of an element will vary with its chemical environment, but it is usually considered to be a transferable property, that is to say that similar values will be valid in a variety of situations.

Caesium is the least electronegative element in the periodic table (=0.79), while fluorine is most electronegative (=3.98). Francium and caesium were originally both assigned 0.7; caesium's value was later refined to 0.79, but no experimental data allows a similar refinement for francium. However, francium's ionization energy is known to be slightly higher than caesium's, in accordance with the relativistic stabilization of the 7s orbital, and this in turn implies that francium is in fact more electronegative than caesium.

Pauling first proposed the concept of electronegativity in 1932 as an explanation of the fact that the covalent bond between two different atoms (A-B) is stronger than would be expected by taking the average of the strengths of the A-A and B-B bonds. According to valence bond theory, of which Pauling was a notable proponent, this "additional stabilization" of the heteronuclear bond is due to the contribution of ionic canonical forms to the bonding.

This is an approximate equation, but holds with good accuracy. Pauling obtained it by noting that a bond can be approximately represented as a quantum mechanical superposition of a covalent bond and two ionic bond-states. The covalent energy of a bond is approximately, by quantum mechanical calculations, the geometric mean of the two energies of covalent bonds of the same molecules, and there is an additional energy that comes from ionic factors, i.e. polar character of the bond.

The geometric mean is approximately equal to the arithmetic mean - which is applied in the first formula above - when the energies are of the similar value, e.g., except for the highly electropositive elements, where there is a larger difference of two dissociation energies; the geometric mean is more accurate and almost always gives a positive excess energy, due to ionic bonding. The square root of this excess energy, Pauling notes, is approximately additive, and hence one can introduce the electronegativity. Thus, it is this semi-empirical formula for bond energy that underlies Pauling electronegativity concept.

The formulas are approximate, but this rough approximation is in fact relatively good and gives the right intuition, with the notion of polarity of the bond and some theoretical grounding in quantum mechanics. The electronegativities are then determined to best fit the data.

In more complex compounds, there is additional error since electronegativity depends on the molecular environment of an atom. Also, the energy estimate can be only used for single, not for multiple bonds. The energy of formation of a molecule containing only single bonds then can be approximated from an electronegativity table, and depends on the constituents and sum of squares of differences of electronegativities of all pairs of bonded atoms. Such a formula for estimating energy typically has relative error of order of 10%, but can be used to get a rough qualitative idea and understanding of a molecule.

R.T. Sanderson has also noted the relationship between Mulliken electronegativity and atomic size, and has proposed a method of calculation based on the reciprocal of the atomic volume. With a knowledge of bond lengths, Sanderson's model allows the estimation of bond energies in a wide range of compounds. Sanderson's model has also been used to calculate molecular geometry, s-electrons energy, NMR spin-spin constants and other parameters for organic compounds. This work underlies the concept of electronegativity equalization, which suggests that electrons distribute themselves around a molecule to minimize or to equalize the Mulliken electronegativity. This behavior is analogous to the equalization of chemical potential in macroscopic thermodynamics.

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 which 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 "ionic character" of a bond to the difference in electronegativity of the two atoms, although this has fallen somewhat into disuse.


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