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Electronegativity

Electronegativity, symbol χ (the Greek letter chi), is a chemical property that describes the tendency of an atom or a functional group to attract electrons (or electron density) towards itself and thus the tendency to form negative ions. An atom's electronegativity is affected by both its atomic number and the distance that its valence electrons reside from the charged nucleus. The higher the associated electronegativity number, the more an element or compound attracts electrons towards it. First proposed by Linus Pauling in 1932 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.

The most commonly used method of calculation is that originally proposed by Pauling. This gives a dimensionless quantity, commonly referred to as the Pauling scale, on a relative scale running from around 0.7 to 3.98 (hydrogen = 2.20). When other methods of calculation are used, it is conventional (although not obligatory) to quote the results on a scale that covers the same range of numerical values: this is known as an electronegativity in Pauling units.

Electronegativity, as it is usually calculated, is not strictly an atomic property, but rather a property of an atom in a molecule: the equivalent property of a free atom is its 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.
The opposite of electronegativity is electropositivity: a measure of an element's ability to donate electrons.

Electronegativities of the elements

Periodic table of electronegativity using the Pauling scale

See also Electronegativities of the elements (data page) and List of electronegativities

Methods of calculation

Pauling electronegativity

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.

The difference in electronegativity between atoms A and B is given by:

\chi_{\rm A} - \chi_{\rm B} = ({\rm eV})^{-1/2} \sqrt{E_{\rm d}({\rm AB}) - [E_{\rm d}({\rm AA}) + E_{\rm d}({\rm BB})]/2}

where the dissociation energies, Ed, of the A–B, A–A and B–B bonds are expressed in electronvolts, the factor (eV)–½ being included to ensure a dimensionless result. Hence, the difference in Pauling electronegativity between hydrogen and bromine is 0.73 (dissociation energies: H–Br, 3.79 eV; H–H, 4.52 eV; Br–Br 2.00 eV)

As only differences in electronegativity are defined, it is necessary to choose an arbitrary reference point in order to construct a scale. Hydrogen was chosen as the reference, as it forms covalent bonds with a large variety of elements: its electronegativity was fixed first at 2.1, later revised to 2.20. It is also necessary to decide which of the two elements is the more electronegative (equivalent to choosing one of the two possible signs for the square root). This is done by "chemical intuition": in the above example, hydrogen bromide dissolves in water to form H+ and Br– ions, so it may be assumed that bromine is more electronegative than hydrogen.

To calculate Pauling electronegativity for an element, it is necessary to have data on the dissociation energies of at least two types of covalent bond formed by that element. Allred updated Pauling's original values in 1961 to take account of the greater availability of thermodynamic data, and it is these "revised Pauling" values of the electronegativity which are most usually used.

Mulliken electronegativity

Mulliken proposed that the arithmetic mean of the first ionization energy and the electron affinity should be a measure of the tendency of an atom to attract electrons. As this definition is not dependent on an arbitrary relative scale, it has also been termed absolute electronegativity, with the units of kilojoules per mole or electronvolts.

However, it is more usual to use a linear transformation to transform these absolute values into values which resemble the more familiar Pauling values. For ionization energies and electron affinities in electronvolts,

\chi = 0.187(E_{\rm i} + E_{\rm ea}) + 0.17 \,

and for energies in kilojoules per mole,

\chi = (1.97\times 10^{-3})(E_{\rm i} + E_{\rm ea}) + 0.19.

The Mulliken electronegativit

Ionic radius

Ionic radius, rion, is a measure of the size of an atom's ion in a crystal lattice. It is measured in either picometres (pm) or Angstrom (Ã…), with 1 Ã… = 100 pm. Typical values range from 30 pm (0.3 Ã…) to over 200 pm (2 Ã…).

The concept of ionic radius was developed independently by Victor Goldschmidt and Linus Pauling in the 1920s to summarize the data being generated by the (at the time) new technique of X-ray crystallography: it is Pauling's approach which proved to be the more influential. X-ray crystallography can readily give the length of the side of the unit cell of a crystal, but it is much more difficult (in most cases impossible, even with more modern techniques) to distinguish a boundary between two ions. For example, it can be readily determined that each side of the unit cell of sodium chloride is 564.02 pm in length, and that this length is twice the distance between the centre of a sodium ion and the centre of a chloride ion:

2[rion(Na+) + rion(Cl−)] = 564.02 pm

However, it is not apparent what proportion of this distance is due to the size of the sodium ion and what proportion is due to the size of the chloride ion. By comparing many different compounds, and with a certain amount of chemical intuition, Pauling decided to assign a radius of 140 pm to the oxide ion O2−, at which point he was able to calculate the radii of the other ions by subtraction.

A major review of crystallographic data led to the publication of a revised set of ionic radii in 1976, and these are preferred to Pauling's original values. Some sources have retained Pauling's reference of rion(O2−) = 140 pm, while other sources prefer to list "effective" ionic radii based on rion(O2−) = 126 pm. The latter values are thought to be a more accurate approximation to the "true" relative sizes of anions and cations in ionic crystals.

The ionic radius is not a fixed property of a given ion, but varies with coordination number, spin state and other parameters. Nevertheless, ionic radius values are sufficiently transferable to allow periodic trends to be recognized. As with other types of atomic radius, ionic radii increase on descending a group. Ionic size (for the same ion) also increases with increasing coordination number, and an ion in a high-spin state will be larger than the same ion in a low-spin state. Anions (negatively charged) are almost invariably larger than cations (positively charged), although the fluorides of some alkali metals are rare exceptions. In general, ionic radius decreases with increasing positive charge and increases with increasing negative charge.

An "anomalous" ionic radius in a crystal is often a sign of significant covalent character in the bonding. No bond is completely ionic, and some supposedly "ionic" compounds, especially of the transition metals, are particularly covalent in character. This is illustrated by the unit cell parameters for sodium and silverhalides in the table. On the basis of the fluorides, one would say that Ag+ is larger than Na+, but on the basis of the chlorides and bromides the opposite appears to be true. This is because the greater covalent character of the bonds in AgCl and AgBr reduces the bond length and hence the apparent ionic radius of Ag+, an effect which is not present in the halides of the more electropositive sodium, nor in silver fluoride in which the fluoride ion is relatively unpolarizable.

Generalization

The concept of ionic radii is based on the assumption of a spherical ion shape. However, from a group-theoretical point of view the assumption is only justified for ions that reside on high-symmetry crystal lattice sites like Na and Cl in halite or Zn and S in sphalerite. A clear distinction can be made, when the point symmetry group of the respective lattice site is considered, which are the cubic groups O6 and Td in NaCl and ZnS. For ions on lower-symmetry sites significant deviations of their electron density from a spherical shape may occur. This holds in particular for ions on lattice sites of polar symmetry, which are the crystallographic point groups C1, C1h, Cn or Cnv, n = 2, 3, 4 or 6. A thorough analysis of the bonding geometry was recently carried out for pyrite-type disulfides, where monovalent chemical bond that involves a metal and a nonmetalion (or polyatomic ions such as ammonium) through electrostatic attraction. In short, it is a bond formed by the attraction between two oppositely charged ions.

The metal donates one or more electrons, forming a positively charged ion or cation with a stable electron configuration. These electrons then enter the non metal, causing it to form a negatively charged ion or anion which also has a stable electron configuration. The electrostatic attraction between the oppositely charged ions causes them to come together and form a bond.

For example, common table salt is sodium chloride. When sodium (Na) and chlorine (Cl) are combined, the sodium atoms each lose an electron, forming cations (Na+), and the chlorine atoms each gain an electron to form anions (Cl−). These ions are then attracted to each other in a 1:1 ratio to form sodium chloride (NaCl).

Na + Cl → Na+ + Cl−→ NaCl

The removal of electrons from the atoms is endothermic and causes the ions to have a higher energy. There may also be energy changes associated with breaking of existing bonds or the addition of more than one electron to form anions. However, the attraction of the ions to each other lowers their energy. Ionic bonding will occur only if the overall energy change for the reaction is favourable – when the bonded atoms have a lower energy than the free ones. The larger the resulting energy change the stronger the bond. The low electronegativity of metals and high electronegativity of non-metals means that the energy change of the reaction is most favorable when metals lose electrons and non-metals gain electrons.

Pure ionic bonding is not known to exist. All ionic compounds have a degree of covalent bonding. The larger the difference in electronegativity between two atoms, the more ionic the bond. Ionic compounds conduct electricity when molten or in solution. They generally have a high melting point and tend to be soluble in water.

Ionic structure

Ionic compounds in the solid state form lattice structures. The two principal factors in determining the form of the lattice are the relative charges of the ions and their relative sizes. Some structures are adopted by a number of compounds; for example, the structure of the rock salt sodium chloride is also adopted by many alkali halides, and binary oxides such as MgO.

Strength of an ionic bond

For a solid crystalline ionic compound the enthalpy change in forming the solid from gaseous ions is termed the lattice energy. The experimental value for the lattice energy can be determined using the Born-Haber cycle. It can also be calculated using the Born-Landé equation as the sum of the electrostatic potential energy, calculated by summing interactions between cations and anions, and a short range repulsive potential energy term. The electrostatic potential can be expressed in terms of the inter-ionic separation and a constant (Madelung constant) that takes account of the geometry of the crystal. The Born-Landé equation gives a reasonable fit to the lattice energy of e.g. sodium chloride where the calculated value is −756 kJ/mol which compares to −787 kJ/mol using the Born-Haber cycle.

Polarization effects

Ions in crystal lattices of purely ionic compounds are spherical; however, if the positive ion is small and/or highly charged, it will distort the electron cloud of the negative ion, an effect summarised in Fajans' rules. This polarization of the negative ion leads to a build-up of extra charge density between the two nuclei, i.e., to partial covalency. Larger negative ions are more easily polarized, but the effect is usually only important when positive ions with charges of 3+ (e.g., Al3+) are involved. However, 2+ ions (Be2+) or even 1+ (Li+) show some polarizing power because their sizes are so small (e.g., LiI is ionic but has some covalent bonding present). Note that this is not the ionic polarization effect which refers to displacement of ions in the lattice due to the application of an electric field.

Ionic versus covalent bonds

In an ionic bond, the atoms are bound by attraction of opposite ions, whereas, in a covalent bond, atoms are bound by sharing electrons. In covalent bonding, the molecular geometry around each atom is determined by VSEPR rules, whereas, in ionic materials, the geometry follows maximum packing rules.

In reality, purely ionic bonds do no


From Yahoo Answers

Question:What is the relationship between electro-negativity and the ionic character of a chemical bond?

Answers:The greater the electronegativity difference, the greater the percent ionic character in a bond. Percent ionic character = 100(1-e^-DEN^2/4))

Question:I would like a website where i can get the conversion chart, or something else. Thanks I am given a bond type, and i am supposed to calculate the elecronegativity difference, and then give the percent ionic character? I already found the electronegativity of all the bond types but i dont how to go about finding the percent ionic character.

Answers:I don't think that this is a meaningful question because there is no magic borderline between ionic and covalent. The maximum EN difference is between F and Fr. This is about 3.6. SO the mid point is 1.8. One could say that above 1.8 it is ionic and covalent below that. However, it is a transition zone. It doesn't simply switch like a traffic light. If you must calculate a percent, use 1.8 or 2.0 as your denominator.

Question:I'm wondering if the amount of a precipitate produced from mixing two ionic solutions will be affected by the difference in electronegativity between the atom of the anion that goes to form the precipitate and the atom of the cation that goes to form the precipitate.

Answers:The electronegativity of an element certainly has a bearing on the percent ionic character in a bond, but that is not the primary factor in the solubility of a compound. By solubility, we are referring to its ability to dissolve and potentially dissociate into ions. Electronegativity alone is not a good predictor of solubility.

Question:The property useful in the prediction of percentage of ionic character in a covalent molecule is 1. electron gain enthalpy 2. electronegativity 3. ionisation potential 4. ionic radii

Answers:Electronegativity. The greater the electronegativity difference between two bonded atoms, the greater the percentage ionic character.