Electronegativity and Bond Polarity

Although we defined covalent bonding as electron sharing, the electrons in a covalent bond are not always shared equally by the two bonded atoms. Unless the bond connects two atoms of the same element, as in H2, there will always be one atom that attracts the electrons in the bond more strongly than the other atom does, as in HCl, shown in Figure \(\PageIndex{1}\). A covalent bond that has an equal sharing of electrons (Figure \(\PageIndex{1a}\)) is called a nonpolar covalent bond. A covalent bond that has an unequal sharing of electrons, as in Figure \(\PageIndex{1b}\), is called a polar covalent bond.

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Figure \(\PageIndex{1}\) Polar versus Nonpolar Covalent Bonds. (a) The electrons in the covalent bond are equally shared by both hydrogen atoms. This is a nonpolar covalent bond. (b) The chlorine atom attracts the electrons in the bond more than the hydrogen atom does, leading to an imbalance in the electron distribution. This is a polar covalent bond.

The distribution of electron density in a polar bond is uneven. It is greater around the atom that attracts the electrons more than the other. For example, the electrons in the H–Cl bond of a hydrogen chloride molecule spend more time near the chlorine atom than near the hydrogen atom. Note that the shaded area around Cl in Figure \(\PageIndex{1b}\) is much larger than it is around H.

This imbalance in electron density results in a buildup of partial negative charge (designated as δ−) on one side of the bond (Cl) and a partial positive charge (designated δ+) on the other side of the bond (H). This is seen in Figure \(\PageIndex{2a}\). The separation of charge in a polar covalent bond results in an electric dipole (two poles), represented by the arrow in Figure \(\PageIndex{2b}\). The direction of the arrow is pointed toward the δ− end while the + tail of the arrow indicates the δ+ end of the bond.

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Figure \(\PageIndex{2}\): (a) Unequal sharing of the bonding pair of electrons between H and Cl leads to partial positive charge on the H atom and partial negative charge on the Cl. Symbols δ+ and δ– indicate the polarity of the H–Cl bond. (b) The dipole is represented by an arrow with a cross at the tail. The cross is near the δ+ end and the arrowhead coincides with the δ–.

Any covalent bond between atoms of different elements is a polar bond, but the degree of polarity varies widely. Some bonds between different elements are only minimally polar, while others are strongly polar. Ionic bonds can be considered the ultimate in polarity, with electrons being transferred rather than shared. To judge the relative polarity of a covalent bond, piersonforcongress.comists use electronegativity, which is a relative measure of how strongly an atom attracts electrons when it forms a covalent bond. There are various numerical scales for rating electronegativity. Figure \(\PageIndex{3}\) shows one of the most popular—the Pauling scale.

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Figure \(\PageIndex{3}\) The electronegativity values derived by Pauling follow predictable periodic trends with the higher electronegativities toward the upper right of the periodic table. Fluorine has the highest value (4.0).

Looking Closer: Linus Pauling

Arguably the most influential piersonforcongress.comist of the 20th century, Linus Pauling (1901–94) is the only person to have won two individual (that is, unshared) Nobel Prizes. In the 1930s, Pauling used new mathematical theories to enunciate some fundamental principles of the piersonforcongress.comical bond. His 1939 book The Nature of the piersonforcongress.comical Bond is one of the most significant books ever published in piersonforcongress.comistry.

By 1935, Pauling’s interest turned to biological molecules, and he was awarded the 1954 Nobel Prize in piersonforcongress.comistry for his work on protein structure. (He was very close to discovering the double helix structure of DNA when James Watson and James Crick announced their own discovery of its structure in 1953.) He was later awarded the 1962 Nobel Peace Prize for his efforts to ban the testing of nuclear weapons.

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Linus Pauling was one of the most influential piersonforcongress.comists of the 20th century.

In his later years, Pauling became convinced that large doses of vitamin C would prevent disease, including the common cold. Most clinical research failed to show a connection, but Pauling continued to take large doses daily. He died in 1994, having spent a lifetime establishing a scientific legacy that few will ever equal.

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The polarity of a covalent bond can be judged by determining the difference in the electronegativities of the two atoms making the bond. The greater the difference in electronegativities, the greater the imbalance of electron sharing in the bond. Although there are no hard and fast rules, the general rule is if the difference in electronegativities is less than about 0.4, the bond is considered nonpolar; if the difference is greater than 0.4, the bond is considered polar. If the difference in electronegativities is large enough (generally greater than about 1.8), the resulting compound is considered ionic rather than covalent. An electronegativity difference of zero, of course, indicates a nonpolar covalent bond.