Electronegativity and Bond Polarity | Chemistry Optional Notes for UPSC PDF Download

Introduction

The electron pairs shared between two atoms are not necessarily shared equally. For example, while the bonding electron pair is shared equally in the covalent bond in  Cl₂ , in  NaCl the 3s electron is stripped from the Na atom and is incorporated into the electronic structure of the Cl atom - and the compound is most accurately described as consisting of individual  Na⁺ and  Cl⁻ ions (ionic bonding). For most covalent substances, their bond character falls between these two extremes. As demonstrated below, the bond polarity is a useful concept for describing the sharing of electrons between atoms within a covalent bond:

• A nonpolar covalent bond is one in which the electrons are shared equally between two atoms.
• A polar covalent bond is one in which one atom has a greater attraction for the electrons than the other atom. If this relative attraction is great enough, then the bond is an ionic bond.

Electronegativity

• The elements with the highest ionization energies are generally those with the most negative electron affinities, which are located toward the upper right corner of the periodic table. Conversely, the elements with the lowest ionization energies are generally those with the least negative electron affinities and are located in the lower left corner of the periodic table.
• Because the tendency of an element to gain or lose electrons is so important in determining its chemistry, various methods have been developed to quantitatively describe this tendency. The most important method uses a measurement called electronegativity (represented by the Greek letter chi, χ, pronounced “ky” as in “sky”), defined as the relative ability of an atom to attract electrons to itself in a chemical compound. Elements with high electronegativities tend to acquire electrons in chemical reactions and are found in the upper right corner of the periodic table. Elements with low electronegativities tend to lose electrons in chemical reactions and are found in the lower left corner of the periodic table.
• Unlike ionization energy or electron affinity, the electronegativity of an atom is not a simple, fixed property that can be directly measured in a single experiment. In fact, an atom’s electronegativity should depend to some extent on its chemical environment because the properties of an atom are influenced by its neighbors in a chemical compound. Nevertheless, when different methods for measuring the electronegativity of an atom are compared, they all tend to assign similar relative values to a given element. For example, all scales predict that fluorine has the highest electronegativity and cesium the lowest of the stable elements, which suggests that all the methods are measuring the same fundamental property.
  • Electronegativity is defined as the ability of an atom in a particular molecule to attract electrons to itself. The greater the value, the greater the attractiveness for electrons.

Electronegativity is a function of:

• the atom's ionization energy (how strongly the atom holds on to its own electrons) and
• the atom's electron affinity (how strongly the atom attracts other electrons).

Both of these are properties of the isolated atom. An element will be highly electronegative if it has a large (negative) electron affinity and a high ionization energy (always endothermic, or positive for neutral atoms). Thus, it will attract electrons from other atoms and resist having its own electrons attracted away.

The Pauling Electronegativity Scale

The original electronegativity scale, developed in the 1930s by Linus Pauling (1901– 1994) was based on measurements of the strengths of covalent bonds between different elements. Pauling arbitrarily set the electronegativity of fluorine at 4.0 (although today it has been refined to 3.98), thereby creating a scale in which all elements have values between 0 and 4.0.

Figure  10.6.1: A Plot of Periodic Variation of Electronegativity with Atomic Number for the First Six Rows of the Periodic Table

The main groups 1 and 2 are purple, the main groups 13 through 18 are green, the transition metals are red, and the lanthanides are blue. Periodic variations in Pauling’s electronegativity values are illustrated in Figures  10.6.1 and 10.6.2. If we ignore the inert gases and elements for which no stable isotopes are known, we see that fluorine (χ=3.98) is the most electronegative element and cesium is the least electronegative nonradioactive element (χ = 0.79). Because electronegativities generally increase diagonally from the lower left to the upper right of the periodic table, elements lying on diagonal lines running from upper left to lower right tend to have comparable values (e.g., O and Cl and N, S, and Br).

The s blocks are purple, the p blocks are green, the d blocks are red, and the f blocks are blue. Electronegativity increase from bottom to top and left to right.

Figure  10.6.2: Pauling Electronegativity Values of the s-, p-, d-, and f-Block Elements. Values for most of the actinides are approximate. Elements for which no data are available are shown in gray. Source: Data from L. Pauling, The Nature of the Chemical Bond, 3rd ed. (1960).

Linus Pauling (1901-1994)

• When he was nine, Pauling’s father died, and his mother tried to convince him to quit school to support the family. He did not quit school, but was later denied a high school degree, and had to work several jobs to put himself through college. Pauling would go on to become one of the most influential chemists of the century if not all time. He won two Nobel Prizes, one for chemistry in 1954 and one for peace in 1962.

• Pauling’s method is limited by the fact that many elements do not form stable covalent compounds with other elements; hence their electronegativities cannot be measured by his method. Other definitions have since been developed that address this problem, e.g., the Mulliken, Allred-Rochow, and Allen electronegativity scales. The Mulliken electronegativity of an element is the average of its first ionization energy and the absolute value of its electron affinity, showing the relationship between electronegativity and these other periodic properties.

Electronegativity Differences between Metals and Nonmetals

• An element’s electronegativity provides us with a single value that we can use to characterize the chemistry of an element. Elements with a high electronegativity (χ ≥ 2.2 in Figure 10.6.2) have very negative affinities and large ionization potentials, so they are generally nonmetals and electrical insulators that tend to gain electrons in chemical reactions (i.e., they are oxidants). 
• In contrast, elements with a low electronegativity (χ≤1.8) have electron affinities that have either positive or small negative values and small ionization potentials, so they are generally metals and good electrical conductors that tend to lose their valence electrons in chemical reactions (i.e., they are reductants). In between the metals and nonmetals, along the heavy diagonal line running from B to At is a group of elements with intermediate electronegativities (χ ~ 2.0). 
• These are the metalloids (or semimetals), elements that have some of the chemical properties of both nonmetals and metals. The distinction between metals and nonmetals is one of the most fundamental we can make in categorizing the elements and predicting their chemical behavior. Figure 10.6.3 shows the strong correlation between electronegativity values, metallic versus nonmetallic character, and location in the periodic table.

Figure  10.6.3: Three-Dimensional Plots Demonstrating the Relationship between Electronegativity and the Metallic/Nonmetallic Character of the Elements. (a) A plot of electrical resistivity (measured resistivity to electron flow) at or near room temperature shows that substances with high resistivity (little to no measured electron flow) are electrical insulators, whereas substances with low resistivity (high measured electron flow) are metals. (b) A plot of Pauling electronegativities for a like set of elements shows that high electronegativity values (≥ about 2.2) correlate with high electrical resistivities (insulators). Low electronegativity values (≤ about 2.2) correlate with low resistivities (metals). Because electrical resistivity is typically measured only for solids and liquids, the gaseous elements do not appear in part (a).

• Metals are blue, semimetals are yellow, nonmetals are gray, gaseous at 20 degrees C are gray with dashed lines. Electronegativity values increase from lower left to upper right in the periodic table.

The rules for assigning oxidation states(opens in new window) are based on the relative electronegativities of the elements; the more electronegative element in a binary compound is assigned a negative oxidation state. As we shall see, electronegativity values are also used to predict bond energies, bond polarities, and the kinds of reactions that compounds undergo.

Solved Examples

Example 1: Based on their positions in the periodic table, arrange Cl, Se, Si, and Sr in order of increasing electronegativity and classify each as a metal, a nonmetal, or a metalloid.
Given: four elements
Asked for: order by increasing electronegativity and classification
Strategy:
(a) Locate the elements in the periodic table. From their diagonal positions from lower left to upper right, predict their relative electronegativities.
(b) Arrange the elements in order of increasing electronegativity.
(c) Classify each element as a metal, a nonmetal, or a metalloid according to its location about the diagonal belt of metalloids running from B to At.
Ans: (a) Electronegativity increases from lower left to upper right in the periodic table (Figure 8.4.2). Because Sr lies far to the left of the other elements given, we can predict that it will have the lowest electronegativity. Because Cl lies above and to the right of Se, we can predict that χ_Cl > χ_Se. Because Si is located farther from the upper right corner than Se or Cl, its electronegativity should be lower than those of Se and Cl but greater than that of Sr.
(b) The overall order is therefore χ_Sr < χ_Si < χ_Se < χ_Cl.
(c) To classify the elements, we note that Sr lies well to the left of the diagonal belt of metalloids running from B to At; while Se and Cl lie to the right and Si lies in the middle. We can predict that Sr is a metal, Si is a metalloid, and Se and Cl are nonmetals.

Example 2: Based on their positions in the periodic table, arrange Ge, N, O, Rb, and Zr in order of increasing electronegativity and classify each as a metal, a nonmetal, or a metalloid.
Ans: Rb < Zr < Ge < N < O; metals (Rb, Zr); metalloid (Ge); nonmetal (N, O)

Percent Ionic Character of a Covalent polar bond

• The two idealized extremes of chemical bonding: (1) ionic bonding—in which one or more electrons are transferred completely from one atom to another, and the resulting ions are held together by purely electrostatic forces—and (2) covalent bonding, in which electrons are shared equally between two atoms. Most compounds, however, have polar covalent bonds, which means that electrons are shared unequally between the bonded atoms. 
• Figure  10.6.4 compares the electron distribution in a polar covalent bond with those in an ideally covalent and an ideally ionic bond. Recall that a lowercase Greek delta (δ) is used to indicate that a bonded atom possesses a partial positive charge, indicated by  δ⁺, or a partial negative charge, indicated by  δ⁻, and a bond between two atoms that possess partial charges is a polar bond.

Figure  10.6.4: The Electron Distribution in a Nonpolar Covalent Bond, a Polar Covalent Bond, and an Ionic Bond Using Lewis Electron Structures. In a purely covalent bond (a), the bonding electrons are shared equally between the atoms. In a purely ionic bond (c), an electron has been transferred completely from one atom to the other. A polar covalent bond (b) is intermediate between the two extremes: the bonding electrons are shared unequally between the two atoms, and the electron distribution is asymmetrical with the electron density being greater around the more electronegative atom. Electron-rich (negatively charged) regions are shown in blue; electron-poor (positively charged) regions are shown in red.

Bond Polarity

• The polarity of a bond—the extent to which it is polar—is determined largely by the relative electronegativities of the bonded atoms. Electronegativity (χ) was defined as the ability of an atom in a molecule or an ion to attract electrons to itself. Thus there is a direct correlation between electronegativity and bond polarity. 
• A bond is nonpolar if the bonded atoms have equal electronegativities. If the electronegativities of the bonded atoms are not equal, however, the bond is polarized toward the more electronegative atom. A bond in which the electronegativity of B (χ_B) is greater than the electronegativity of A (χ_A), for example, is indicated with the partial negative charge on the more electronegative atom: (10.6.1)

• One way of estimating the ionic character of a bond—that is, the magnitude of the charge separation in a polar covalent bond—is to calculate the difference in electronegativity between the two atoms: Δ_χ = χ_B − χ_A.
• To predict the polarity of the bonds in Cl₂, HCl, and NaCl, for example, we look at the electronegativities of the relevant atoms: χ_Cl = 3.16, χ_H = 2.20, and χ_Na = 0.93. Cl₂ must be nonpolar because the electronegativity difference (Δχ) is zero; hence the two chlorine atoms share the bonding electrons equally. In NaCl, Δχ is 2.23. This high value is typical of an ionic compound (Δχ ≥ ≈1.5) and means that the valence electron of sodium has been completely transferred to chlorine to form Na⁺ and Cl⁻ ions. In HCl, however, Δχ is only 0.96. The bonding electrons are more strongly attracted to the more electronegative chlorine atom, and so the charge distribution is

Remember that electronegativities are difficult to measure precisely and different definitions produce slightly different numbers. In practice, the polarity of a bond is usually estimated rather than calculated.

• Bond polarity and ionic character increase with an increasing difference in electronegativity.

As with bond energies, the electronegativity of an atom depends to some extent on its chemical environment. It is therefore unlikely that the reported electronegativities of a chlorine atom in NaCl, Cl₂, ClF₅, and HClO₄ would be exactly the same.

Dipole Moments

The asymmetrical charge distribution in a polar substance such as HCl produces a dipole moment where  Qr in meters (m). is abbreviated by the Greek letter mu (µ). The dipole moment is defined as the product of the partial charge Q on the bonded atoms and the distance r between the partial charges:
μ = Qr (10.6.2)
where Q is measured in coulombs (C) and r in meters. The unit for dipole moments is the debye (D):
1D = 3.3356 × 10⁻³⁰C⋅⋅m (10.6.3)
When a molecule with a dipole moment is placed in an electric field, it tends to orient itself with the electric field because of its asymmetrical charge distribution (Figure  10.6.4).
Figure  10.6.5: Molecules That Possess a Dipole Moment Partially Align Themselves with an Applied Electric Field. In the absence of a field (a), the HCl molecules are randomly oriented. When an electric field is applied (b), the molecules tend to align themselves with the field, such that the positive end of the molecular dipole points toward the negative terminal and vice versa.

We can measure the partial charges on the atoms in a molecule such as HCl using Equation  10.6.2. If the bonding in HCl were purely ionic, an electron would be transferred from H to Cl, so there would be a full +1 charge on the H atom and a full −1 charge on the Cl atom. The dipole moment of HCl is 1.109 D, as determined by measuring the extent of its alignment in an electric field, and the reported gas-phase H–Cl distance is 127.5 pm. Hence the charge on each atom is
(10.6.4)
By dividing this calculated value by the charge on a single electron (1.6022 × 10⁻¹⁹ C), we find that the electron distribution in HCl is asymmetric and that effectively it appears that there is a net negative charge on the Cl of about −0.18, effectively corresponding to about 0.18 e⁻. This certainly does not mean that there is a fraction of an electron on the Cl atom, but that the distribution of electron probability favors the Cl atom side of the molecule by about this amount.

(10.6.5)

To form a neutral compound, the charge on the H atom must be equal but opposite. Thus the measured dipole moment of HCl indicates that the H–Cl bond has approximately 18% ionic character (0.1811 × 100), or 82% covalent character. Instead of writing HCl as

we can therefore indicate the charge separation quantitatively as

Our calculated results are in agreement with the electronegativity difference between hydrogen and chlorine χ_H = 2.20; χ_Cl = 3.16, χ_Cl − χ_H = 0.96), a value well within the range for polar covalent bonds. We indicate the dipole moment by writing an arrow above the molecule. Mathematically, dipole moments are vectors, and they possess both a magnitude and a direction. The dipole moment of a molecule is the vector sum of the dipoles of the individual bonds. In HCl, for example, the dipole moment is indicated as follows:
The arrow shows the direction of electron flow by pointing toward the more electronegative atom. The charge on the atoms of many substances in the gas phase can be calculated using measured dipole moments and bond distances. Figure  10.6.6 shows a plot of the percent ionic character versus the difference in electronegativity of the bonded atoms for several substances. According to the graph, the bonding in species such as NaCl(g) and CsF(g) is substantially less than 100% ionic in character. As the gas condenses into a solid, however, dipole–dipole interactions between polarized species increase the charge separations. In the crystal, therefore, an electron is transferred from the metal to the nonmetal, and these substances behave like classic ionic compounds. The data in Figure  10.6.6 show that diatomic species with an electronegativity difference of less than 1.5 are less than 50% ionic in character, which is consistent with our earlier description of these species as containing polar covalent bonds. The use of dipole moments to determine the ionic character of a polar bond is illustrated in Example  10.6.2.
Figure  10.6.6: A Plot of the Percent Ionic Character of a Bond as Determined from Measured Dipole Moments versus the Difference in Electronegativity of the Bonded Atoms.In the gas phase, even CsF, which has the largest possible difference in electronegativity between atoms, is not 100% ionic. Solid CsF, however, is best viewed as 100% ionic because of the additional electrostatic interactions in the lattice.

Solved Examples

Example 1: In the gas phase, NaCl has a dipole moment of 9.001 D and an Na–Cl distance of 236.1 pm. Calculate the percent ionic character in NaCl.
Given: chemical species, dipole moment, and internuclear distance
Asked for: percent ionic character
Strategy:
(a) Compute the charge on each atom using the information given and Equation  10.6.2.
(b) Find the percent ionic character from the ratio of the actual charge to the charge of a single electron.
Ans: (a) The charge on each atom is given by
Thus NaCl behaves as if it had charges of 1.272 × 10−19 C on each atom separated by 236.1 pm.
(b) The percent ionic character is given by the ratio of the actual charge to the charge of a single electron (the charge expected for the complete transfer of one electron):

Example 2: In the gas phase, silver chloride (AgCl) has a dipole moment of 6.08 D and an Ag–Cl distance of 228.1 pm. What is the percent ionic character in silver chloride?
Ans: 55.5%

Summary

• Bond polarity and ionic character increase with an increasing difference in electronegativity. The electronegativity (χ) of an element is the relative ability of an atom to attract electrons to itself in a chemical compound and increases diagonally from the lower left of the periodic table to the upper right.
• The Pauling electronegativity scale is based on measurements of the strengths of covalent bonds between different atoms, whereas the Mulliken electronegativity of an element is the average of its first ionization energy and the absolute value of its electron affinity. Elements with a high electronegativity are generally nonmetals and electrical insulators and tend to behave as oxidants in chemical reactions. Conversely, elements with a low electronegativity are generally metals and good electrical conductors and tend to behave as reductants in chemical reactions.
• Compounds with polar covalent bonds have electrons that are shared unequally between the bonded atoms. The polarity of such a bond is determined largely by the relative electronegativites of the bonded atoms. The asymmetrical charge distribution in a polar substance produces a dipole moment, which is the product of the partial charges on the bonded atoms and the distance between them.