The absolute value of the difference in electronegativity (ΔEN) of two bonded atoms provides a rough measure of the polarity to be expected in the bond and, thus, the bond type. When the difference is very small or zero, the bond is covalent and nonpolar. When it is large, the bond is polar covalent or ionic. The absolute values of the electronegativity differences between the atoms in the bonds H–H, H–Cl, and Na–Cl are 0 (nonpolar), 0.9 (polar covalent), and 2.1 (ionic), respectively.
The degree to which electrons are shared between atoms varies from completely equal (pure covalent bonding) to not at all (ionic bonding).
The best guide to the covalent or ionic character of a bond is to consider the types of atoms involved and their relative positions in the periodic table.
Some compounds contain both covalent and ionic bonds. The atoms in polyatomic ions, such as OH–, NO3−, and NH4+, are held together by polar covalent bonds. However, these polyatomic ions form ionic compounds by combining with ions of the opposite charge. For example, potassium nitrate, KNO3, contains the K+ cation and the polyatomic NO3− anion. Thus, bonding in potassium nitrate is ionic, resulting from the electrostatic attraction between the ions K+ and NO3−, as well as covalent between the nitrogen and oxygen atoms in NO3−.
As discussed previously, polar covalent bonds connect two atoms with differing electronegativities, leaving one atom with a partial positive charge (δ+) and the other atom with a partial negative charge (δ–), as the electrons are pulled toward the more electronegative atom. This separation of charge gives rise to a bond dipole moment. The magnitude of a bond dipole moment is represented by the Greek letter mu (µ) and is given by the formula shown here, where Q is the magnitude of the partial charges (determined by the electronegativity difference) and r is the distance between the charges:
This bond moment can be represented as a vector, a quantity having both direction and magnitude. Dipole vectors are shown as arrows pointing along with the bond from the less electronegative atom toward the more electronegative atom. A small plus sign is drawn on the less electronegative end to indicate the partially positive end of the bond. The length of the arrow is proportional to the magnitude of the electronegativity difference between the two atoms.
A whole molecule may also have a separation of charge, depending on its molecular structure and the polarity of each of its bonds. If such a charge separation exists, the molecule is said to be a polar molecule (or dipole); otherwise, the molecule is said to be nonpolar. The dipole moment measures the extent of net charge separation in the molecule as a whole. The dipole moment is determined by adding the bond moments in three-dimensional space, taking into account the molecular structure.
For diatomic molecules, there is only one bond, so it’s bond dipole moment determines the molecular polarity. Homonuclear diatomic molecules such as Br2 and N2 have no difference in electronegativity, so their dipole moment is zero. For heteronuclear molecules such as CO, there is a small dipole moment. For HF, there is a larger dipole moment because there is a larger difference in electronegativity.
When a molecule contains more than one bond, the geometry must be taken into account. If the bonds in a molecule are arranged such that their bond moments cancel (vector sum equals zero), then the molecule is nonpolar. This is the situation in CO2. Each of the bonds is polar, but the molecule as a whole is nonpolar. From the Lewis structure, and using VSEPR theory, the CO2 molecule is determined to be linear with polar C=O bonds on opposite sides of the carbon atom. The bond moments cancel because they are pointed in opposite directions. In the case of the water molecule, the Lewis structure again shows that there are two bonds to a central atom, and the electronegativity difference again shows that each of these bonds has a nonzero bond moment. In this case, however, the molecular structure is bent because of the lone pairs on O, and the two bond moments do not cancel. Therefore, water does have a net dipole moment and is a polar molecule (dipole).
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