2.2.

4 Electronegativity When two atoms form a covalent bond, they do not share the electrons equally unless the atoms are identical. The concept ofelectronegativitywas introduced by Linus Pauling to explain the tendency of an atom in a molecule to attract electrons. The basis for Paulings numerical scale that describes this property lies in the fact that polar covalent bonds between atoms of different electronegativity are more stable than if they were purely covalent. The stabilization of the bond,AB, in a diatomic molecule AB due to this effect can be expressed as ABDAB1=2DAADBB 2:15

whereDAAandDBBrepresent the bond energies in the diatomic species A2and B2, respectively, and DABis the bond energy of the molecule AB. Thus, the term AB represents the additional contribution to the AB bond strength as a result of the atoms having different electronegativities. The extent of the stabilization can also be expressed in terms of the difference in the electronegativities of the atoms by the equation ABkJ mol 1 96:48jA B j 2 2:16 whereAandBare the electronegativities for atoms A and B. Therefore, it is thedifference between the electronegativities that is related to the additional stabilization of the bond, but some value for the electronegativity for at least one atom had to be specified. Assigning a

value for one atom leads to arelativevalue for each other atom. The Pauling electronegativity scale was established with fluorine being given a value of 4.0, and the other atoms then have values between 0 and 4. Table 2.4 shows electronegativity values for several atoms. The electronegativity scale established by Pauling is not the only such scale, and the electronegativity of an atom A has been defined by Mulliken as A 1=2IE 2:17

Where I and E are the ionization potential and electron affinity of the atom. This is a reasonable approach because the ability of an atom in a molecule to attract electrons would be expected to be related to the ionization potential and electron affinity. Both of these properties are also related to the ability of an atom to attract electrons. Most electronegativities on the Mulliken scale differ only slightly from the Pauling values. For example, fluorine has the Pauling electronegativity of 4.0 and a value of 3.91 on the Mulliken scale. A different approach was used by Allred and Rochow to establish an electronegativity scale. This scale is based on a consideration of the electrostatic force holding a valence shell electron in an atom of radius,r, by an effective nuclear charge, Z*. This electronegativity value,AR, is given by AR0:359Z

=r 2 0:744 2:18 Many other electronegativity scales have been developed, but the three scales described are the ones most frequently used, and qualitative agreement between the scales is quite good. One of the most important uses of electronegativity values is in deciding bond polarities and in estimating the importance of possible resonance structures for molecules. For example, based on electronegativities, HCl should have hydrogen at thepositiveend of the dipole and chlorine at thenegativeend. In drawing structures for molecules, it will be observed that those structures corresponding to an accumulation of electron density on atoms of high electronegativity are usually more important. This situation will be treated more fully in the next section.

Electronegativity and Bonding in Solids The other class I teach on a regular basis is Chemistry 121 (the first quarter of freshman chemistry). Today we are going to go back to some of the bonding concepts introduced in that course and examine them in greater detail. One of the things that we teach the freshman is that bonding interactions can be characterized into one of the following categories:

Covalent Bonding Metallic Bonding Ionic Bonding Dispersion Forces (i.e. van der Waals interactions, dipole-dipole interactions, etc.)

Of course we dont spend too much time to mention that most bonding interactions do not fall neatly into the above categories, rather they involve mixtures of the various types of bonding. We have seen that the Coulombic interactions, from which ionic bonding is derived, are optimized by the following combination of atomic and structural characteristics:

Large net charges on anions and cations Large coordination numbers High symmetry

In contrast, covalent bonding is dependent upon the degree of spatial and energetic overlap between atomic orbitals on neighboring atoms. It is favored by the following atomic and structural characteristics:

Neutral atoms (or at least minimal net charges on the atoms) Tetrahedral coordination (at least for main group elements) High symmetry

Metallic bonding goes hand in hand with the following atomic and structural characteristics:

Neutral atoms Close packed structures (large coordination number) High symmetry

In our last lecture we saw how the bonding interactions in the group IVA (14) solids change from covalent to metallic as we move the down the periodic table. This results from a decrease in the orbital overlap as the principle quantum number increases, and leads to a dramatic change in physical properties (color, electrical conductivity, hardness, etc.) as we go from diamond to lead. Today we are going to examine the progression from purely covalent bonding to largely ionic bonding. Mixed ionic covalent character is present in any bond between two atoms of different types. The parameter which is used to quantify the degree of The power of an atom in a molecule to attract electrons to

Electronegativity itself.

Our use of electronegativity as a tool for quantifying the ionic and covalent contributions to a bond follows directly from its definition. As the electronegativity difference between two atoms increases the bonding electrons are increasingly drawn toward the more electronegative atom. When the electronegativity difference becomes extreme the electrons are really no longer shared but can be thought of being transferred from the cation to the anion (ionic bonding). In Chem 121 we use the following arbitrary cutoffs to differentiate covalent and ionic bonding: > 2 Ionic Bonding 0.5 < < 2 Polar Covalent Bonding < 0.5 Covalent Bonding

Although these rules give beginners a feel for the scale (the Pauling scale) and use of electronegativity, one should realize that there is no sharp cutoff between ionic and covalent bonding. Rather it is a smooth transition between the two. The importance of electronegativity in solid state chemistry is illustrated by its use as a parameter in structure sorting maps. For example, as we discussed in the last lecture the work of Philips and Van Vechten which showed that for binary AX compounds the structure type evolves from: Sphalerite Wurtzite Rock Salt as we increase the ionic character of the bonding. Another way to state this would be to say that this structural progression (Sphalerite to Rock Salt) takes place as the electronegativity difference increases. A somewhat simpler route to the same conclusion is the structure sorting approach of Mooser and Pearson. In the map below the difference in electronegativity is plotted on the x axis and the average principle quantum number of the valence shell on the y axis. Once again we see that as the ionic character of the bonds increases (greater and larger n) the observed structure type evolves from Sphalerite to

Wurtzite to Rock Salt to CsCl. [Insert Mooser-Pearson plot of AB compounds] In a similar manner we can understand the structures adopted by AX2 compounds. Fluorite structure Cation Anion coordination coordination number number = = 4 8 (cubic) (tetrahedral)

Madelung constant = 5.04 Rutile structure Cation Anion coordination coordination number number = = 3 6 (trigonal (octahedral) planar)

Madelung constant = 4.82 CdCl2 and CdI2 structures These differ from rutile and fluorite in that anion layers are stacked on top of each other with cations present only between alternating layers of anions. The presence of neighboring anion layers (with no cations in between) is extremely unfavorable from a Coulombic point of view. Even though both structures are rather unfavorable from an ionic standpoint, the CdCl2 is slightly better due to the fact that the Cd ion

positions are staggered from one layer to the next, which results in longer Cd-Cd distances. From the above arguments we would expect that as the ionic component of the bonding interaction increases we should see the following structural evolution: CdI2 CdCl2 Rutile Fluorite Examining several series of MX2 compounds we see the following: Compound ZnI2 ZnBr2 ZnCl2 ZnF2 1.01 1.31 1.51 2.33 Structure CdI2/CdCl2 CdCl2 CdCl2 Rutile Compound MgI2 MgBr2 MgCl2 MgF2 1.35 1.65 1.85 2.67 Structure CdI2 CdI2 CdCl2 Rutile

CdI2 CdBr2 CdCl2 CdF2

0.97 1.27 1.47 2.29

CdI2 CdCl2 CdCl2 Fluorite

CaI2 CaBr2 CaCl2 CaF2

1.66 1.96 2.16 2.98

CdI2 Rutile Rutile Fluorite

Differences in electronegativity dictate not only structure type, but physical properties as well. It has been shown that the band gap of binary AX compounds increases as the electronegativity difference increases. In this way we can use electronegativity to predict whether a compound will be an insulator or a semiconductor. [Scan in figure 4.22 from Huhey] Hopefully I have convinced you that electronegativity is a powerful concept, now lets take a look at a variety of methods for estimating electronegativity (for it cannot be directly measured). Pauling Electronegativity Pauling was the first person to propose the concept of electronegativity and suggest a method for estimating its value. His derivation of electronegativity can be

understood by considering the bonding in Cl2, F2 and ClF. The bond energies of these molecules are 2.51 eV, 1.59 eV and 2.64 eV respectively. He reasoned that the covalent bonding interaction in Cl-F should be the average of the Cl-Cl and F-F bond strengths, which would be (2.51 + 1.59)/2 = 2.05 eV. However, we see that the bond strength in Cl-F is much higher (2.64). Pauling postulated that the excess bond enthalpy can be attributed to the ionic interaction between the two atoms, which he called the ionic resonance energy. He then defined the difference in electronegativity between Cl and F to be equal to the square root of the ionic resonance energy: F) Cl) = sqrt (2.64 eV 2.05 eV) = 0.77 One of the most important take home lessons from Paulings concept of electronegativity is that an interaction containing mixed ionic-covalent character can be stronger than either a pure covalent or a pure ionic bond. Chemists are sometimes guilty of assuming that the strength of a bond increases as the covalent character of the bond increases, which is not generally true. Mulliken Electronegativity The Mulliken electronegativity of an atom is probably the simplest, and can be easily calculated for most atoms. Mulliken proposed that the electronegativity should be an average of the ionization energy and electron affinity of an atom, Sanderson Electronegativity Sandersons electronegativity scale is based on the principle that the ability of an atom or ion to attract electrons to itself is dependent upon the effective nuclear charge felt by the outermost valence electrons. It is a well known fact that as the effective nuclear charge increases the size of the atom decreases. It becomes more compact. Sanderson reasoned that the electronegativity, S, should be proportional to the compactness of an atom. Specifically: = D/Da where D is the electron density of an atom (its atomic number divided by its atomic volume (covalent radius cubed)) and Da is the expected electron density of an atom, calculated from extrapolation between the noble gas elements. Values of Sanderson electronegativities are given in Table 2.10 of West. One of the most important contributions that Sanderson made to our understanding of electronegativity is his "principle of electronegativity equalization". This principle can be stated as follows: = [EA+IE]/2.

Principle of Electronegativity Equalization When two or more atoms initially different in electronegativity combine chemically, they adjust to have the same intermediate electronegativity within the
*

compound.

This

intermediate

electronegativity is given by the geometric mean of the individual electronegativities of the component atoms.
*

The geometric mean of n numbers is obtained by multiplying all of the numbers

together and taking the nth root of the product. In other words the electron density will flow from the more electropositive atom to the more electronegative atom, creating a partial positive charge on the former and a partial negative charge on the latter. As the positive charge on the electropositive atom increases, its effective nuclear charge increases, hence its electronegativity increases. The same trend happens in the opposite direction for the more electronegative atom, until the two have the same electronegativity. Example Use Sandersons principle of electronegativity equalization to calculate the electronegativity of SnO2 and SrTiO3. S(SnO2) = (SSn SO2)1/3 = (4.28 4.902)1/3 = 4.68 S(SrTiO3) = (SSr STi SO3)1/5 = (1.28 2.09 4.903)1/5 = 3.16 It should be noted that although the idea of electronegativity equalization was developed by Sanderson, it is valid to use it with other electronegativity scales. Sanderson used his electronegativity scale and concept of electronegativity equalization to calculate partial charges and ionic radii of atoms in ionic-covalent compounds and molecules. The basic conclusion he reaches is that the partial ionic charge and ionic radius of an ion are not constants, but vary considerably depending upon the electronegativity of the surrounding atoms. Furthermore, Sandersons calculations suggest that the partial charge on an atom never exceeds +1 or 1. Once again reinforcing the idea that oxidation states do not reflect the true charge of an ion. Details regarding the Sanderson system are given in chapter 2 of West or in more detail in Sandersons own writings (Chemical Periodicity (1961) and Chemical B onds and Bond Energy (1976) by R.T. Sanderson).

Electronegativity
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Atoms and Molecules - Periodic Trends

Electronegativity increases as you move across the periodic table from left to right. This occurs due to a greater charge on the nucleus, causing the electron bonding pairs to be very attracted to atoms placed further right on the periodic table. Fluorine is the most electronegative element. Electronegativity decreases as you move down the periodic table. This is caused by an increased amount of shielding, or screening, by the innermost electrons. As you move down the table more electrons are added between the nucleus and the bonding pair, causing the effective nuclear charge to be less. The increase in distance between the nucleus and the bonding pair decreases the attraction between the two.

Electronegativity scales The concept of electronegativity was first introduced by Linus Pauling in the 1930s as a means of describing bond energies. Bond energies of polar bonds (formed by atoms with different electronegativities) are larger than the average of the bond energies of the two homonuclear species. For example, HC1 has a bond energy of 428 kJ/mol, compared to a calculated value of 336 kJ/mol, the average of the bond energies of H2 (432 kJ/mol) and C12 (240 kJ/mol). From data like these, Pauling calculated electronegativity values that could be used to predict other bond energies. More recent val-

ues have come from other molecular properties and from atomic properties, such as ionization energy and electron affinity. Regardless of the method of calculation, the scale used is usually adjusted to give values near those of Pauling to allow better comparison. Table 3-4 summarizes approaches used for determining different scales. Principal Authors Method of Calculation or Description Pauling 10 Bond energies Mulliken Average of electron affinity and ionization energy Allred & Rochow 12 Electrostatic attraction proportional to 2*/r2 Smderson 13 Electron dcnsitics of atoms Pearson 14 Average of electron affinity and ionization energy Allen 15 Average energy of valence shell electrons, configuration energies ~aff6l Orbital electronegativities