Bonding

Covalent and metallic bonding

Objectives
• Classify bonding as intermolecular and
intramolecular (chemical) bonding
• Relate bonding to position (group) of elements in
the periodic table
• Discuss three types of chemical bonding
▫ Ionic/electrovalent
▫ Covalent
▫ Metallic
• Explain chemical bonding diagrams
Covalent bond
• Between non-metal + non-metal
• Sharing of electrons (single/double/triple)
▫ When this happens there is an electrostatic
attraction between the nuclei (which are
positively charged) and the pair of shared
electrons (which are negatively charged).
How many bonds can atoms make?
• The number of bonds that an atom can form can
often be predicted from the number of electrons
needed to reach an octet
▫ Each atom of a group 4 element has four valence
electrons and thus requires four more electrons
to reach an octet.
 They form four covalent bonds
▫ Group 5 elements have five valence electrons they
form three covalent bonds.
▫ Group 6 elements obtain an octet by forming two
covalent bonds.
▫ Group 7 elements have seven valence electrons and
can obtain an octet by forming one covalent bond.
 How many bonds can atoms make?
• The number of bonds an atom can form depends on its
valence electrons.
• The number of valence electrons is equal to the group
number in the Periodic Table
Group 4 Group 5 Group 6 Group 1
Learning check
State the number of bonds that each atom can make.
 Learning check explained
• Phosphorus and sulfur, which are in period 3, and because
the valence shell of elements in periods 3 and higher can
hold more than eight electrons, these elements do not
always follow the octet rule.
▫ Phosphorus can stably possess eight or 10 valence electrons,
and sulfur can stably possess eight, 10, or 12 valence
electrons.
• Octet expansion indicates that an atom’s valence shell
contains more than eight electrons
Types of covalent bonds
• Types of covalent bonds:
▫ Non-polar covalent bond
 Equal sharing of electrons
 E.g. Cl2, H2, F2 } diatomic molecules
▫ Polar covalent bond
 Unequal sharing of electrons
 E.g. HCl, H2O, NH3
▫ Coordinate/dative covalent bond
 Electron shared from one atom
 E.g. NH4+
Non-polar covalent bond

If the atoms that form a covalent bond are identical, as in H2, Cl2, and other diatomic
molecules, then the electrons in the bond must be shared equally. We refer to this as
a pure covalent bond. Electrons shared in pure covalent bonds have an equal
probability of being near each nucleus
Polar covalent bond
• When the atoms linked by a covalent bond are
different, the bonding electrons are shared, but no
longer equally.
▫ Instead, the bonding electrons are more attracted to
one atom than the other, giving rise to a shift of
electron density toward that atom.
▫ This unequal distribution of electrons is known as
a polar covalent bond, characterized by a partial
positive charge on one atom and a partial negative
charge on the other.
• The atom that attracts the electrons more
strongly acquires the partial negative charge and
vice versa.
▫ 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.
▫ Thus, in an HCl molecule, the chlorine atom
carries a partial negative charge and the hydrogen
atom has a partial positive charge.
Polar covalent
• Atoms with different electronegativities
▫ Separation of charge
 E.g
 H2O

 HCl, NH3, H2S

All ionic bonds → polar!!!

 Electronegativity (EN)
• Whether a bond is nonpolar or polar covalent is
determined by a property of the bonding atoms
called electronegativity.
▫ Electronegativity is a measure of the tendency of an
atom to attract electrons (or electron density) towards
itself.
▫ It determines how the shared electrons are distributed
between the two atoms in a bond.
▫ The more strongly an atom attracts the electrons in its
bonds, the larger its electronegativity.
▫ Electrons in a polar covalent bond are shifted toward the
more electronegative atom; thus, the more electronegative
atom is the one with the partial negative charge.
▫ The greater the difference in electronegativity, the more
polarized the electron distribution and the larger the partial
charges of the atoms.
EN: Pauling scale
• Linus Pauling proposed electronegativity values of
elements.
▫ In general, electronegativity increases from left to right
across a period in the periodic table and decreases down a
group.
▫ Thus, the nonmetals, which lie in the upper right, tend to
have the highest electronegativities, with fluorine the
most electronegative element of all (EN = 4.0).
▫ Metals tend to be less electronegative elements, and
the group 1 metals have the lowest electronegativities.
• Note that noble gases are excluded from this figure
because these atoms usually do not share electrons with
others atoms since they have a full valence shell.
• Electronegativity describes how tightly an atom
attracts electrons in a bond.
• It is a dimensionless quantity that is calculated,
not measured.
EN and bond type
• 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.
 is large, the bond is polar covalent or ionic.
• 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.
▫ Bonds between two nonmetals are generally covalent;
bonding between a metal and a nonmetal is often ionic.
• 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 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−.
• This table is just a general guide, however, with many exceptions.
▫ For example, the H and F atoms in HF have an electronegativity
difference of 1.9, and the N and H atoms in NH3 a difference of 0.9, yet
both of these compounds form bonds that are considered polar covalent.
▫ Likewise, the Na and Cl atoms in NaCl have an electronegativity
difference of 2.1, and the Mn and I atoms in MnI2 have a difference of
1.0, yet both of these substances form ionic compounds.
 Key concepts
• Covalent bonds form when electrons are shared between atoms
and are attracted by the nuclei of both atoms.
• In pure covalent bonds, the electrons are shared equally.
• In polar covalent bonds, the electrons are shared unequally, as
one atom exerts a stronger force of attraction on the electrons
than the other.
• The ability of an atom to attract a pair of electrons in a chemical
bond is called its electronegativity.
• The difference in electronegativity between two atoms
determines how polar a bond will be.
• In a diatomic molecule with two identical atoms, there is no
difference in electronegativity, so the bond is nonpolar or pure
covalent.
• When the electronegativity difference is very large, as is the
case between metals and nonmetals, the bonding is
characterized as ionic.
 Coordinate/dative covalent bond
• A co-ordinate bond (also called a dative covalent
bond) is a covalent bond (a shared pair of electrons)
in which both electrons come from the same atom.
▫ E.g. the reaction between ammonia and hydrochloric
acid
 NH3 + HCl → NH4Cl
• Representing coordinate bond:
▫ A co-ordinate bond is shown by an arrow.
▫ The arrow points from the atom donating the lone
pair to the atom accepting it:
 • NH3 + BF3 →

Using lines to represent the bonds, the coordinate bond could be drawn more
simply as:
• Carbon monoxide
▫ CO has a triple bond that consists of:
 Two covalent bonds between the carbon and oxygen
atoms
 One dative covalent bond using a lone pair on the
oxygen atom:
Macromolecules
• Covalent compounds
• Atoms arranged in crystalline pattern
▫ Each atom → covalently bonded to neighboring
atoms
 E.g graphite, diamond → C-atom at lattice point
▫ Giant molecules
 High MPs and BPs
Metallic bond
• Metals tend to have high melting points and boiling
points suggesting strong bonds between the atoms.
• Metallic bonding is often described as an array of
positive ions in a sea of electrons.
• The metallic bond is the electrostatic
attraction between these free-moving
(delocalised) electrons and positive metal cations.
Metallic bond
• Is a metal made up of atoms or ions?
▫ It is made of atoms.
▫ Each positive center in the diagram represents all
the rest of the atom apart from the outer electron,
but that electron has not been lost - it may no longer
have an attachment to a particular atom, but it's still
there in the structure.
▫ Sodium metal is therefore written as Na, not Na+.
Metallic bond
• The Electron Sea Model:
▫ Positive atomic nuclei (brown circles) surrounded
by a sea of delocalized electrons (yellow circles).
• Use the sea of electrons model to explain why
Magnesium has a higher melting point (650 °C)
than sodium (97.79 °C).
▫ Magnesium has two outer shell electrons.
▫ Both of these electrons become delocalized, so the
"sea" has twice the electron density as it does in
sodium.
 The remaining "ions" also have twice the charge and so
there will be more attraction between "ions" and "sea".
 Thus, metallic bond strength is directly proportional to
the number of mobile electrons
▫ Magnesium atoms also have a slightly smaller radius
than sodium atoms, and so the delocalized electrons
are closer to the nuclei
 Metallic bond strength increases with decreasing size of
metal atom
Molten metals
• What about metallic bond in molten metals?
▫ Metallic bond is still present
▫ But, ordered structure has been broken down