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Chemistry LibreTexts

8.5: Electronegativity

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  • Page ID
    98638
  • Skills to Develop

    • To define electronegativity and bond polarity
    • To recognize the periodic trend in electronegativities of the elements

    Both ionization energy and electron affinity give us an idea of the tendency of different atoms to hold onto their electrons or attract new ones, respectively. This idea that different elements have different amounts of attraction for electrons is also the basis for the important property of electronegativity. Unlike ionization energy and electron affinity, however, electronegativity is not a property of atoms by themselves, but rather of atoms when they participate in chemical bonds. In chemical bonds, the electrons shared between two atoms are not necessarily shared equally.  For example, while an electron pair is shared equally in the covalent bond in \(Cl_2\), 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. Electronegativity values help us to make predictions about the polarity of chemical bonds in which the attraction for electrons between the two atoms is not equal.

    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 as a single number. The most important method is to use 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:

    1. the atom's ionization energy (how strongly the atom holds on to its own electrons) and
    2. 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 \(\PageIndex{1}\): Left: A Plot of Periodic Variation of Electronegativity with Atomic Number for the First Six Rows of the Periodic Table. Right: A Three-Dimensional Plot of the Trend in Electronegativity in the Periodic Table. 

    Periodic variations in Pauling’s electronegativity values are illustrated in Figures \(\PageIndex{1}\) and \(\PageIndex{2}\). If we ignore the inert gases and elements for which no stable isotopes are known, we see that fluorine (\(\chi = 3.98\)) is the most electronegative element and cesium is the least electronegative nonradioactive element (\(\chi = 0.79\)). 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).

     

    Figure \(\PageIndex{2}\): 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)

    Linus Pauling is the only person to have received two unshared (individual) Nobel Prizes: one for chemistry in 1954 for his work on the nature of chemical bonds and one for peace in 1962 for his opposition to weapons of mass destruction. He developed many of the theories and concepts that are foundational to our current understanding of chemistry, including electronegativity and resonance structures.

    Linus Pauling made many important contributions to the field of chemistry. He was also a prominent activist, publicizing issues related to health and nuclear weapons.

    Pauling also contributed to many other fields besides chemistry. His research on sickle cell anemia revealed the cause of the disease—the presence of a genetically inherited abnormal protein in the blood—and paved the way for the field of molecular genetics. His work was also pivotal in curbing the testing of nuclear weapons; he proved that radioactive fallout from nuclear testing posed a public health risk.

    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 \(\PageIndex{2}\)) 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 (\(\chi \le 1.8\)) 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 \(\PageIndex{3}\) shows the strong correlation between electronegativity values, metallic versus nonmetallic character, and location in the periodic table.

    Figure \(\PageIndex{3}\): 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).

    Electronegativity values increase from lower left to upper right in the periodic table.

    The rules for assigning oxidation states 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.

    Example \(\PageIndex{1}\): Increasing Electronegativity

    On the basis of 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:
    1. Locate the elements in the periodic table. From their diagonal positions from lower left to upper right, predict their relative electronegativities.
    2. Arrange the elements in order of increasing electronegativity.
    3. 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.

    Solution:

    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 χCl > χSe. 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 χSr < χSi < χSe < χCl.

    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.

    Exercise \(\PageIndex{1}\)

    On the basis of 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.

    Answer

    Rb < Zr < Ge < N < O; metals (Rb, Zr); metalloid (Ge); nonmetal (N, O)

    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.