The electron affinity of an atom or molecule is defined as the amount of energy released when an [1] electron is added to a neutral
atom or molecule to form a negative ion. X+e X
This property is measured for atoms and molecules in the gaseous state only, since in the solid or liquid states their energy levels would be changed by contact with other atoms or molecules. A list of the electron affinities was used by Robert S. Mulliken to develop an electronegativity scale for atoms, [2][3] equal to the average of the electron affinity and ionization potential. Other theoretical concepts that use electron affinity include electronic chemical potential and chemical hardness. Another example, a molecule or atom that has a more positive value of electron affinity than another is often called an electron acceptor and the less positive anelectron donor. Together they may undergo charge-transfer reactions. In solids, the electron affinity is the energy difference between the vacuum energy and the conduction [4] band minimum. To use electron affinities properly, it is essential to keep track of sign. For any reaction that releases energy, the change in energy, E, has a negative value and the reaction is called an exothermic process. Electron capture for almost all non-noble gas atoms involves the release of [5] energy and thus are exothermic. The positive values that are listed in tables of Eea are amounts or magnitudes. It is the word, released within the definition energy released that supplies the negative sign. Confusion arises in mistaking Eea for a change in energy, E, in which case the positive values listed in tables would be for an endo- not exo-thermic process. The relation between the two is, Eea = - E(attach). However, if the value assigned to Eea is negative, the negative sign implies a reversal of direction, and energy is required to attach an electron. In this case, the electron capture is an endothermic process and the relationship, Eea = - E(attach) is still valid. Negative values typically arise for the capture of a second electron, but also for the nitrogen atom. Electronegativity, symbol , is a chemical property that describes the tendency of an atom or [1] a functional group to attract electrons (or electron density) towards itself. 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 [2] 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 Linus 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 a property of an atom, but rather a property of [3] 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. On the most basic level, electronegativity is determined by factors like the nuclear charge (the more protons an atom has, the more "pull" it will have on negative electrons) and the number/location of other electrons present in the atomic shells (the more electrons an atom has, the farther from the nucleus the valence electrons will be, and as a result the less positive charge they will experienceboth because of their increased distance from the nucleus, and because the other electrons in the lower energy core orbitals will act to shield the valence electrons from the positively charged nucleus). The opposite of electronegativity is electropositivity: a measure of an element's ability to donate electrons.
[4]
