Chapter 5 - CHEMICAL BONDING

Chemical bonding

Chemical bonds
Chemical bonds are the connections between atoms in a molecule. These bonds include both
strong intramolecular interactions, such as covalent and ionic bonds. They are related to
weaker intermolecular forces, such as dipole-dipole interactions, the London dispersion forces,
and hydrogen bonding. The weaker forces will be discussed in a later concept.

Chemical bonds: This picture shows examples of chemical bonding using Lewis dot notation
of Hydrogen, carbon, water and acetylene. In water, there is a single bond between each
hydrogen and oxygen. Bonds, especially covalent bonds, are often represented as lines
between bonded atoms. Acetylene has a triple bond, a special type of covalent bond that will be
discussed later.

Covalent Bonds

Chemical bonds are the forces of attraction that tie atoms together. Bonds are formed when
valence electrons, the electrons in the outermost electronic “shell” of an atom, interact. The
nature of the interaction between the atoms depends on their relative electronegativity. Atoms
with equal or similar electronegativity form covalent bonds, in which the valence electron
density is shared between the two atoms. The electron density resides between the atoms and
is attracted to both nuclei. This type of bond forms most frequently between two non- metals.
When there is a greater electronegativity difference than between covalently bonded atoms, the
pair of atoms usually forms a polar covalent bond. The electrons are still shared between the
atoms, but the electrons are not equally attracted to both elements. As a result, the electrons
tend to be found near one particular atom most of the time. Again, polar covalent bonds tend
to occur between non-metals.

Ionic Bonds

Finally, for atoms with the largest electronegativity differences (such as metals bonding with
nonmetals), the bonding interaction is called ionic, and the valence electrons are typically
represented as being transferred from the metal atom to the nonmetal. Once the electrons
have been transferred to the non-metal, both the metal and the non-metal are considered to be
ions. The two oppositely charged ions attract each other to form an ionic compound.

Bonds, Stability, and Compounds

Covalent interactions are directional and depend on orbital overlap, while ionic interactions have
no particular directionality. Each of these interactions allows the atoms involved to gain eight
electrons in their valence shell, satisfying the octet rule and making the atoms more stable.
These atomic properties help describe the macroscopic properties of compounds. For example,
smaller covalent compounds that are held together by weaker bonds are frequently soft and
malleable. On the other hand, longer-range covalent interactions can be quite strong, making
their compounds very durable. Ionic compounds, though composed of strong bonding
interactions, tend to form brittle crystalline lattices.

Ionic Bonds

Ionic bonds are a subset of chemical bonds that result from the transfer of valence electrons,
typically between a metal and a nonmetal.
 valence electrons: The electrons of an atom that can participate in the formation of
chemical bonds with other atoms. They are the furthest electrons from the nucleus.
 octet rule: An atom is most stable when there are eight electrons in its valence shell.

Forming an Ion

Ionic bonds are a class of chemical bonds that result from the exchange of one or more valence
electrons from one atom, typically a metal, to another, typically a nonmetal. This electron
exchange results in an electrostatic attraction between the two atoms called an ionic bond. An
atom that loses one or more valence electrons to become a positively charged ion is known as a
cation, while an atom that gains electrons and becomes negatively charged is known as an
anion.
This exchange of valence electrons allows ions to achieve electron configurations that mimic
those of the noble gases, satisfying the octet rule. The octet rule states that an atom is most
stable when there are eight electrons in its valence shell. Atoms with less than eight electrons
tend to satisfy the duet rule, having two electrons in their valence shell. By satisfying the duet
rule or the octet rule, ions are more stable.
A cation is indicated by a positive superscript charge (+ something) to the right of the atom. An
anion is indicated by a negative superscript charge (- something) to the right of the atom. For
example, if a sodium atom loses one electron, it will have one more proton than electron, giving
it an overall +1 charge. The chemical symbol for the sodium ion is Na +1 or just Na+. Similarly, if
a chlorine atom gains an extra electron, it becomes the chloride ion, Cl –. Both ions form
because the ion is more stable than the atom due to the octet rule.

Forming an Ionic Bond

Once the oppositely charged ions form, they are attracted by their positive and negative
charges and form an ionic compound. Ionic bonds are also formed when there is a large
electronegativity difference between two atoms. This difference causes an unequal sharing of
electrons such that one atom completely loses one or more electrons and the other atom gains
one or more electrons, such as in the creation of an ionic bond between a metal atom (sodium)
and a nonmetal (fluorine).
Formation of sodium fluoride: The transfer of electrons and subsequent attraction of
oppositely charged ions.

Determining the Formula of an Ionic Compound

To determine the chemical formulas of ionic compounds, the following two conditions must be
satisfied:
1. Each ion must obey the octet rule for maximum stability.
2. Ions will combine in a way that the overall ionic compound will be neutral. In other
words, the charges of the ions must balance out.
Magnesium and fluorine combine to form an ionic compound. What is the formula for the
compound?
Mg most commonly forms a 2+ ion. This is because Mg has two valence electrons and it would
like to get rid of those two ions to obey the octet rule. Fluorine has seven valence electrons and
usually forms the F – ion because it gains one electron to satisfy the octet rule. When Mg 2+ and
F – combine to form an ionic compound, their charges must cancel out. Therefore, one
Mg2+ needs two F – ions to neutralize the charge. The 2+ of the Mg is balanced by having two -
1 charged ions. Therefore, the formula of the compound is MgF2. The subscript two indicates
that there are two fluorines that are ionically bonded to magnesium.
On the macroscopic scale, ionic compounds form crystalline lattice structures that are
characterized by high melting and boiling points and good electrical conductivity when melted
or solubilized.

Example

Magnesium and fluorine combine to form an ionic compound. What is the formula for the
compound?
Mg most commonly forms a 2+ ion. This is because Mg has two valence electrons and it would
like to get rid of those two ions to obey the octet rule. Fluorine has seven valence electrons and
as such, usually forms the F– ion because it gains one electron to satisfy the octet rule. When
Mg2+ and F– combine to form an ionic compound, their charges must cancel out. Therefore, one
Mg2+ needs two F– ions to balance. The 2+ of the Mg is balanced by having two -1 charged
ions. Therefore, the formula of the compound is MgF2. The subscript two indicates that there
are two fluorine that are ionically bonded to magnesium.

Covalent Bonds

Covalent bonding involves two atoms, typically nonmetals, sharing valence electrons.
Forming Covalent Bonds

Covalent bonds are a class of chemical bonds where valence electrons are shared between two
atoms, typically two nonmetals. The formation of a covalent bond allows the nonmetals to obey
the octet rule and thus become more stable. For example:

 A fluorine atom has seven valence electrons. If it shares one electron with a carbon atom
(which has four valence electrons), the fluorine will have a full octet (its seven electrons
plus the one it is sharing with carbon).
 Carbon will then have five valence electrons (its four and the one its sharing with
fluorine). Covalently sharing two electrons is also known as a “single bond.” Carbon will
have to form four single bonds with four different fluorine atoms to fill its octet. The
result is CF4 or carbon tetrafluoride.
Covalent bonding requires a specific orientation between atoms in order to achieve the overlap
between bonding orbitals. Covalent bonding interactions include sigma-bonding ( σ) and pi-
bonding (π). Sigma bonds are the strongest type of covalent interaction and are formed via the
overlap of atomic orbitals along the orbital axis. The overlapped orbitals allow the shared
electrons to move freely between atoms. Pi bonds are a weaker type of covalent interactions
and result from the overlap of two lobes of the interacting atomic orbitals above and below the
orbital axis.

Covalent bonds can be single, double, and triple bonds.

 Single bonds occur when two electrons are shared and are composed of one sigma bond
between the two atoms.
 Double bonds occur when four electrons are shared between the two atoms and consist
of one sigma bond and one pi bond.
 Triple bonds occur when six electrons are shared between the two atoms and consist of
one sigma bond and two pi bonds (see later concept for more info about pi and sigma
bonds).

Ionic Compounds vs. Molecular Compounds

Unlike an ionic bond, a covalent bond is stronger between two atoms with similar
electronegativity. For atoms with equal electronegativity, the bond between them will be a non-
polar covalent interaction. In non-polar covalent bonds, the electrons are equally shared
between the two atoms. For atoms with differing electronegativity, the bond will be a polar
covalent interaction, where the electrons will not be shared equally.

Ionic solids are generally characterized by high melting and boiling points along with brittle,
crystalline structures. Covalent compounds, on the other hand, have lower melting and boiling
points. Unlike ionic compounds, they are often not soluble in water and do not conduct
electricity when solubilized.

Note: Please visit flash drive and read the PDF file and video clip entitled “chemical Bonds
review”, “non-polar and polar”, and “ionic and covalent compounds”, for better understanding.

Chapter summary

Bond Classifications

Chemical bonds are the attractive forces that hold atoms together in the form of compounds. A
chemical bond is formed when electrons are shared between two atoms. There are three types
of bonds: covalent bonds, polar covalent bonds and ionic bonds. The simplest example
of bonding is demonstrated by the H 2 molecule. We can see that each hydrogen atom has a
single electron from the periodic table. If two hydrogen atoms come together to form a bond,
then each hydrogen atom effectively has a share in both electrons and thus each resembles an
inert gas structure. The two electrons that are shared are considered to be a chemical bond and
can be represented with either two dots or a single dash between the two bonded atoms.

Covalent Bond: A covalent bond is formed when there is an equal sharing of electrons

between two atoms. The atoms forming a covalent bond must have relatively equal attraction
for the electrons. The bonds between the carbon atom and the hydrogen atoms in the
compound methane CH4 are examples of covalent bonds between two different elements.

Polar covalent bond: If the atoms differ in their attraction for electrons, a polar-covalent
bond will be formed. Water is an example of a molecule with this type of bond.

The attraction of electrons to the nucleus of an atom is a very important property of atoms and
is called electronegativity. The difference in electronegativity between bonded atoms
determines the bond polarity, which is determined by the relative difference in
electronegativity between two atoms that are joined together by a chemical bond. A dipole
results from an unequal distribution of the electron pair in the bond between the atoms.

Ionic bonds: An ionic bond is formed when an electron is essentially transferred from one
atom of a pair to the other creating ions. Sodium chloride is an example of a compound with
this type of bond. These compounds exist as a crystal lattice with all the ions stacked in definite
patterns. The following picture is a representation of a cubic crystal of sodium chloride. The
chloride ions are represented by the purple spheres.

Remember that a cation is a positively charged atom or molecule (one that has lost one or
more electrons) and that an anion is a negatively charged atom or molecule (one that has
gained one or more electrons). The ions are held together by electrostatic attractions. Ionic
compounds have high melting points and many are soluble in water.

Most compounds that contain metals are ionic. For the purpose of this course, you may assume
that all compounds that contain metals are ionic. If a compound contains the ammonium ion, it
will be ionic. That is why the compound ammonium nitrate is written as NH 4NO3 rather than
N2H4O3. This alerts people to the fact that the compound contains the ammonium group and the
nitrate group.
Methods of Showing Formulas of Compounds

 Molecular formulas show only the type and number of atoms in a molecule.

 Structural formulas show the atoms in their correct placement in the molecule.
 Electron-dot formulas are similar to structural formulas but also include all of the
non-bonding outer electrons. Knowledge of electron placement aids in understanding
how molecules and elements react with one another.

Drawing Electron-Dot Formulas

Step 1: Sum up the total number of valence electrons for the elements in the molecule. If the
molecule is charged, subtract one electron for each positive charge or add one electron for each
negative charge.

Step 2: Write the structure for the molecule with a pair of electrons (or a dash) between each
atom. Groups of atoms will usually have the less electronegative atom surrounded by atoms
having greater electronegativity. Never place a hydrogen atom in the center since it can only
form one bond. Think about the valence of each atom and make sure that these valences are
not exceeded except in the case of ions. Ions always have more or less bonds than the normal
uncharged atom. The common valence or number of bonds formed for some common atoms
are:

 H=1
 O and S = 2
 N=3
 C=4
 F, Cl, Br and I = 1

Step 3: Place electrons around the outer atoms to fill their outer shells. Most atoms require
eight electrons (the octet rule) so they will resemble an inert gas. Elements in  Group I to Group
13 often do not follow the octet rule and have less than eight electrons in the final formula.

Step 4: Subtract the number of electrons used so far from the total calculated in Step 1 and
place these remaining electrons on the central atom or atoms.

Step 5: If the central atom ends up with less than 8 electrons, then it probably forms a multiple
bond with an adjacent outer atom.

Step 6: Finally you should calculate the formal charge on the atoms.

Example 1: Methane CH4

The first electron-dot formula we shall draw will be methane, CH 4.

Step 1: The first thing that you must do is to determine the number of electrons available for
the formula.

 Hydrogen is a Group 1 element and thus has 1 valance electron. Since there are 4
hydrogen atoms, the total for hydrogen will be 4 electrons.
 Carbon is in Group 14 element thus has 4 outer electrons (remember that we don't use
the atomic number for electron-dot formulas).

The total number of electrons for all atoms is 8.

Step 2: The next step is to determine which atom will be in the center of the molecule.
Hydrogen atoms are only able to form one bond to other atoms so we need to put the carbon
atom in the center.

Step 3: The next step requires drawing a "C" and "H" and place 2 electrons between these
atoms.

Step 4: All you have to do now is draw all of the other hydrogen atoms around the carbon atom
and place 2 electrons between these hydrogen atoms and the carbon atom. This gives you a
total of 8 electrons and you have drawn the electron-dot formula for methane.

Step 5: A full octet. No further effort needed.

Step 6: Calculating the Formal Charges for elements in methane.

The formal charge for each hydrogen atom is calculated by the following calculation...

fc=1−12(2)−0=0(1)(1)fc=1−12(2)−0=0

The first number represents the Roman Numeral over the periodic table column. The
number "2" in the parentheses represents the shared electrons and there are no non-
bonding electrons so the last number is zero.

The formal charge for the carbon atom is calculated by the following calculation...

fc=4−12(8)−6=1(2)(2)fc=4−12(8)−6=1

Example 2: Water H2O

Then let's try a compound that has non-bonding electron pairs: water.

Step 1: The first thing that you must do is to determine the number of electrons available for
the formula.

 Hydrogen is a Group 1 element and thus has 1 valance electron. Since there are 2
hydrogen atoms, the total for hydrogen will be 2 electrons.
 Oxygen is a Group 16 element thus has 6 outer electrons (remember that we don't use
the atomic number for electron-dot formulas).

The total number of electrons for all atoms is 8.

Step 2: The next step is to determine which atom will be in the center of the molecule.
Hydrogen atoms are only able to form one bond to other atoms so we need to put the oxygen
atom in the center.
Step 3: The next thing that you must do is to draw an "O" and "H" and place 2 electrons
between these atoms.

Step 4: Now repeat this with the second "H". Don't worry about where these atoms are
positioned around the oxygen atom, it does not matter for this representation.

Step 5: Now all you have to do is place the remaining 4 electrons on the oxygen atom. The
hydrogen atoms can only share in 2 electrons so don't put more electrons around them. This
gives you a total of 8 electrons and you have drawn the electron-dot formula for water.

Step 6: Calculating the Formal Charge for atoms in water.

The formal charge for the hydrogen atom is calculated by the following calculation...

fc=1−12(2)−0=0(3)(3)fc=1−12(2)−0=0

The first number represents the Roman Numeral over the periodic table column. The
number "2" in the parentheses represents the shared electrons and there are no non-
bonding electrons so the last number is zero.

The formal charge for the oxygen atom is calculated by the following calculation...

fc=6−12(2)−4=1(4)(4)fc=6−12(2)−4=1

Example 3: Hydroxide Ion

The next example will be an ion with a negative charge, the hydroxide ion, HO−HO−.

Step 1: The first thing that you must do is to determine the number of electrons available for
the formula?

 Hydrogen is is a Group 1 element and thus has 1 electron.

 Oxygen is a Group 16 element and thus has 6 outer electrons.
 We must add one electron for the negative charge.

The total number of electrons for both atoms including the extra electron for the negative
charge is 8.

Step 2: Draw the hydrogen atom next to the oxygen atom and place a pair of electrons
between the atoms.
Step 3: The last thing needed to complete the formula is to place the remaining 6 electrons
around the oxygen atom.

Step 6: Calculating the Formal Charge for the Hydroxide Ion, HO−HO−.

The formal charge for the hydrogen atom is calculated by the following calculation...

fc=1−12(2)−0=0(5)(5)fc=1−12(2)−0=0

The first number represents the Roman Numeral over the periodic table column. The
number "2" in the parentheses represents the shared electrons and there are no non-
bonding electrons so the last number is zero.

The formal charge for the oxygen atom is calculated by the following calculation...

fc=6−12(2)−6=1(6)(6)fc=6−12(2)−6=1

Example 4: Ammonium Ion

Now let's see what happens when we have a positive charge and draw the ammonium ion,
NH4+.

Step 1: The first thing that you must do is to determine the number of electrons available for
the formula?

 Hydrogen is a Group 1 element and thus has 1 electron. Since there are 4 hydrogen
atoms, we have 4 electrons.
 Nitrogen is is a Group 15 element and thus has 5 outer electrons.
 We must subtract one electron for the positive charge.

The total number of electrons for all atoms including the loss of an electron for the
positive charge is 8.

Steps 2-5: Draw the nitrogen atom in the center and place the 4 hydrogen atoms around it.
Draw a pair of electrons between each pair. This actually finishes the formula. Notice that this
structure looks exactly like the structure for methane except that the center atom is a nitrogen
atom. When two structures have identical electron-dot formulas, they are considered to
be isoelectronic.

Step 5:

The formal charge for each of the atoms is calculated by the following calculation:
 fc=1−12(2)−0=0(7)(7)fc=1−12(2)−0=0

The first number represents the Roman Numeral over the periodic table column. The
number "2" in the parentheses represents the shared electrons and there are no non-
bonding electrons so the last number is zero.

The formal charge for the nitrogen atom is calculated by the following calculation:

fc=5−12(8)−6=+1(8)(8)fc=5−12(8)−6=+1

Example 5: Molecular Oxygen

Finally, let's draw a compound that requires multiple bonds and draw the formula for oxygen,
O2.

Step 1: The first thing that you must do is to determine the number of electrons available for
the formula?

 Oxygen is a Group 16 element and thus has 6 outer electrons...since there are 2 oxygen
atoms, there will be a total of 12 electrons.

Step 2: Draw the 2 oxygen atoms with a pair of electrons between them.

Step 3: The next thing that you must do is to draw the remaining electrons in pairs around each
of the oxygen atoms giving neither atom more than 8 total electrons.

Step 4: The oxygen atom on the right has 8 electrons but the oxygen atom on the left has only
6 electrons. The only way to correct this problem is to create a multiple bond between the
oxygen atoms. Take a pair of electrons from the oxygen atom on the right and place this pair
between the 2 atoms.

Step 6: Calculating the Formal Charges for elements in methane.

The formal charge for each oxygen atom is calculated by the following calculation...

fc=6−12(2)−4=0(9)(9)fc=6−12(2)−4=0

The first number represents the Roman Numeral over the periodic table column. The
number "2" in the parentheses represents the shared electrons and there are no non-
bonding electrons so the last number is zero.