Electronegativities from bond energies

If we select any bond between unlike atoms from the table above, calling such a bond A—B, it appears that the energy of this A—B bond is almost always greater than the geometric mean of the energies of bonds A—A and B—B. Three examples are listed  

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Calculation of electronegativities from bond energies requires averaging over a number of compounds to cancel out experimental uncertainties and other minor effects. Methods that use ionization energies and other atomic properties can be calculated more directly. The electronegativities reported here and in Appendix B-4 are suitable for most uses, but the actual values for atoms in molecules may differ from this average, depending on their electronic environment. 

Bond Energies and the Relative Electronegativity of Atoms.—In Table II there are collected the energies of single bonds obtained in the preceding sections. One additional value, obtained by a method to be described later, is also included 1.44 v. e. for N N. Under each bond energy is given the value for a normal covalent bond, calculated from additivity, and below that the difference A. It is seen that A is positive in twenty of the twenty-one cases. The exception, C I, may be due to experimental error, and be not real. 

Electronegativity measures how strongly an atom attracts the electrons in a chemical bond. This property of an atom involved in a bond is related to but distinct from ionization energy and electron affinity. As described in Chapter 8, ionization energy measures how strongly an atom attracts one of its own electrons. Electron affinity specifies how strongly an atom attracts a free electron. Figure 9 6 provides a visual summary of these three... 

Like bond lengths, bond energies result from the interplay of several factors, including nuclear charge, principal quantum number, electrical forces, and electronegativity. Thus, it should not be surprising that there are numerous... 

When the counterion is complex, for example metal-halogen anions such as BF4-, the most electronegative portion of the counterion becomes attached to the silicon center. Because of this attachment, it is natural to consider the intermediacy of a silicenium cation (silylium or silylenium ion) intermediate in such reactions (Eq. 4). Bond energies derived from electron impact studies indicate that Eq. 4 is exothermic in the gas phase by about 8 kcal/mol.26,29 There seems little doubt that trivalent silicon-centered cationic species do exist in the gas phase30,31 or that processes similar to that shown in Eq. 4 do occur there.32,33... 

Pauling based electronegativity values on bond energies between atoms, but that is not the only way to approach the problem of the ability of atoms in a molecule to attract electrons. For example, the ease of removing an electron from an atom, the ionization potential, is related to its ability to attract electrons to itself. The electron affinity also gives a measure of the ability of an atom to hold on to an electron that it has gained. These atomic properties should therefore be related to the ability of an atom in a molecule to attract electrons. Therefore, it is natural to make use of these properties in an equation... 

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