Module 2: Ionic and Covalent Bonding

At the end of the course the student should be able to:

- Discuss and illustrate how atoms combine with each other and form chemical bonds
- Predict the properties of the covalent bond
- Use Lewis structure to represent bonding of atoms and electron distribution in a molecule / ion
-Assign formal charges on the atoms after chemical combination

Chemical Bonds

- forces that hold atoms together

Elements gain, lose or share electrons in order to attain the electronic configuration of the most
stable elements, the noble elements (which has an octet of electrons, except He which has two
electrons in the outermost energy level).

1. Ionic Bond- formed by the transfer of electrons from a metal to a non-metal.

Example:

Na (atomic no. is 11) Cl (atomic no. is 17)

Na= 1s2 2s2 2p6 3s1 (IA) 1s2 2s2 2p6 3s2 3p5 (VIIA)

When Na loses one electron, its electronic configuration is 1s2 2s2 2p6 3so (Na-1e- = Na+)

When Cl gains one electron, its electronic configuration is 1s2 2s2 2p6 3s2 3p6 (Cl + 1e- = Cl-)

Na+ is now isoelectronic with the noble element, Ne( atomic no. of 10)

Cl- is now isoelectronic with the noble element, Ar ( atomic no. of 18)

Na+ + Cl- = NaCl<---- ionic compound formed

One possible formation of ionic compounds is the combination of metal and non-metal. Metals
easily lose electrons while nonmetals gain electrons. In the periodic table, metals are present in
IA, IIA and some of the IIIA elements and the B Family. In the case of non-metals these are
mostly located in IVA, VA, VIA, and VIIA. For the representative elements, like Na, one would
notice that the metal loses its valence electron to attain the electronic configuration of the stable
element, like Ne. For the non-metals like Cl it gains one electron to attain the electronic
configuration of the stable element, Ar. Valence electrons are identified by the group number of
the element. For example, Na belongs to IA, then it has only one valence electron to lose and
the resulting ion (Na+ with 10 e) becomes stable. To predict the number of electrons gained by
the non-metal, we follow the “Octet Rule”, non-metals gain electrons so that the total number of
valence electrons will be equal to that of the noble elements (except which is eight (8).
For example, if you have the following combinations what would be the predicted products:

Na + S ----------🡪

Ca + Cl ------- >

Al + O -----🡪

Answer:

One would notice that metals lose all the valence electrons whereas non-metals gain enough electrons
to attain the octet. Ionic compounds can also be a combination of the following:

Metal + polyatomic ion : 2 Na+ + SO42- -------- > Na2SO4

Polyatomic ion + polyatomic ion: NH4+ + NO3-1 --🡪 NH4NO3

Polyatomic ion + nonmetal: NH4++ Cl-1---- > NH4Cl

I. Nomenclature of Inorganic Compounds

Oxidation Number or Oxidation State - the charge that an atom has or appears to have when
certain arbitrary rules are applied; oxidation numbers are useful in identifying atoms that are
oxidized (loss of electrons) or reduced (gain of electrons).
Rules:

1. Any element in its free state has an oxidation number of zero

2. Metals generally have positive oxidation numbers (e.g. Na+, K+, Li+ Ca2+, Mg2+, Au+, Au 3+

3. The oxidation number of hydrogen in a compound or an ion is generally +1. An exception is a

metal hydride when hydrogen is second in the formula and has an oxidation number of -1 (e.g.
NaH ( H = -1); HCl (H=-1)).

4. The oxidation number of oxygen in a compound or an ion is generally -2, with the exception
of the peroxide where it is -1 (e.g. H2O2)

5. The oxidation number of a monatomic ion is the same as the charge on the ion (e.g. Cl-1,
Mg2+).

6. The algebraic sum of the oxidation numbers for all the atoms in a compound must equal zero.

7. The algebraic sum of the oxidation numbers for all the atoms in a polyatomic ion must equal
the charge on the ion.

Steps to find the oxidation number for an element within a compound:

1. Write the oxidation number of each known atom below the atom in the formula.

2. Multiply each oxidation number by the number of atoms of that element in the compound.

3. Write an equation indicating the sum of all the oxidation numbers in the compound or ion.
Using Ions to Write Formulas

In writing the formula of a compound the algebraic sum of the oxidation numbers should be
equal to zero. Elements or ions with positive oxidation numbers are written first followed by
elements or ions with negative oxidation numbers.

Examples:

Na+ + F- ------> NaF sum of oxidation numbers: +1 + -1=0

Ca2+ + F- --------> CaF sum of oxidation numbers: +2 + -1 = -1, not the correct formula

Ca2+ + 2F- -----> CaF2 sum of oxidation numbers: +2 + -1 x 2= 0

Na+ + SO42- ----> Na2SO4

B. Naming Binary Compounds

1. Metal with Fixed Oxidation State (e.g. IA, IIA, IIIA)- Name the metal and change the ending
of the non-metal to –ide (e.g. NaCl = sodium chloride)

2. Metal with Varying Oxidation State – Determine the oxidation state of cation.

Common Name – Use –ous for lower oxidation state and –ic for higher oxidation state (e.g. Fe2+
= Ferrous; Fe3+ = Ferric)

FeCl3 is named Ferric chloride

Stock System – Use Roman numeral to indicate oxidation number (e.g. Au+1 = Gold (I); Au3+ =
Gold (III)

AuCl3 is named Gold (III) chloride

3. Binary Compounds Containing Two Nonmetals- Use Greek prefixes to indicate number of
atoms for each element. (e.g. 1 – mono; 2-di; 3-tri; 4-tetra; 5-penta)

P2O5 – Diphosphorus pentoxide

S2F10 – Disulfur decafluoride

NH3 – Ammonia (exception to the rule)

4. Exceptions that Use -ide Endings: Hydroxides (OH-); Cyanide (CN-); Ammonium (NH 4+1)

5. Binary Acids: Hydro +-ic + acid

e.g. HCl = Hydrochloric acid

C. Naming Ternary Compounds

Polyatomic Ions:

SO42- (sulfate), SO32- (sulfite) PO43- (Phosphate), PO33- (Phosphite) NO3- (Nitrate), NO2-
(Nitrate) CO32- (Carbonate), HCO3- (Bicarbonate), C2O4-2 (Oxalate)
CrO41- (Chromate), Cr2O72- (Dichromate), ClO42- (Perchlorate), ClO3- (Chlorate),
ClO2-(Chlorite), ClO- (Hypochlorite), OH- (Hydroxide), CN- (Cyanide), S2O32- (Thiosulfate),
AsO43- (Arsenate), MnO4- (Permanganate)

2. Covalent Bond

- sharing of electrons (usually between nonmetals)

Example:

Carbon element belongs to family IVA, so it has four valence electrons. Its tendency is to gain
four more electrons to attain an octet of electrons just like the noble elements. What will be the
structure if it bonds with a hydrogen atom?

Hydrogen atoms can only attain the electronic configuration of He because it has only one
electron. Since nonmetals share electrons, the carbon atom will share its electron with 4 H
atoms to attain the octet . In the case of H each hydrogen atom attains the electronic
configuration of He.

C + 4H -----> CH4<----- possible compound

Example:

Nitrogen atom belongs to VA so it needs 3 more electrons to attain the octet, so N can bond with
3 hydrogen atoms to attain the octet

N + 3H -----> NH3<------ Ammonia

3. Lewis Structures

Rules:

1. Add the valence electrons from all the atoms. For polyatomic anion, add the negative charges
to the total; for polyatomic cations subtract no. of positive charges from the total.

2. Identify the central atom (usually the least electronegative atom or atom with higher
covalency no.).

3. Draw a single covalent bond between the central atom and each of the surrounding atoms.
Arrange the remaining electrons to satisfy the duet rule for hydrogen and the octet rule for the
second-row elements.
4. If the octet rule is not satisfied for the central atom, try adding double or triple bonds between
the surrounding atoms and the central atom, using the lone pairs from the surrounding atoms.

Example:

Write the Lewis structure of CH4, NH3, CO2, CO32-

CH4

First, Identify the central atom. Usually the one that exists alone except H. If there are more
than one central atom that exists alone, then choose the one that is less electronegative or the
one with the highest convalency no (the no. of bonds that the atom can have to attain the octet).
Here are the common covalency of central atoms:

Rule 1: the total no. of valence electrons in methane is 8: C = 1C x 4 val e = 4; H = 4H x 1 val e = 4)

Rule 2: the central atom is C

Rule 3: Draw a single covalent bond around the central atom, take note that it should follow the octet.

Following the covalency no. of C, the structure would look like this:

Following the same procedure, NH3 will have a structure like this:

In period 2, elements such as C, N, O and F can attain the rule of 8 e. B which belongs to period 2 but
with only 3 valence electrons is exception to the octet rule

For CO2, the central atom C, does not have enough electrons to complete the octet; so in order to
complete the octet double bonds are introduced which imply that electrons from the surrounding atom
in this case O, are transferred towards the carbon thus double bonds are formed.

Three cases can be constructed that do not follow the Octet Rule, and as such, they are known as the
exceptions to the Octet Rule. Following the Octet Rule for Lewis Dot Structures leads to the most
accurate depictions of stable molecular and atomic structures and because of this we always want to use
the octet rule when drawing Lewis Dot Structures. However, it is hard to imagine that one rule could be
followed by all molecules. There is always an exception, and in this case, three exceptions. The Octet
Rule is violated in these three scenarios:

When there are an odd number of valence electrons, e.g. NO

When there are too few valence electrons; e.g. BH3

When there are too many valence electrons e g. SO42-

Lewis Structure and Formal Charge

Formal charges are an important book-keeping device that we use in Lewis structures. They tell us if one
atom is donating extra electrons to another to give it an octet. If an atom needs to donate more
electrons than normal in order for everyone to get an octet, it will have a positive formal charge. If an
atom donates fewer electrons than normal and everyone still has an octet, it must be getting extra
electrons from somewhere else. It will have a negative formal charge. Formal charge is often present if
the atom does not have its usual number of bonds. Valence rules can act as flags to alert you that formal
charges are present. Let us illustrate this using the Lewis structure of CO32-. Formal charge of an atom is
computed as follows:

Formal Charge (FC)= Group no.-lone pairs- ½ of the shared electrons

= Group no.- total no. of valence e-(after cutting the bond)

Hybridized Structure

FC of O (single bond) = 6-6-1 or 6-7 = -1

FC of C (central atom) = 4-4(after cutting all the bonds that surround the carbon)= 0

Resonance Structure

In carbonate ions, one would notice that the sum of the charges is equal to -2 which is the charge of the
anion. Secondly, carbonate can be written in three Lewis structures with different positions of the
double bonds. Structures which differ only in the position of the electrons but not the atoms are what
we call resonance structures. So carbonate has three resonance structures. The true structure of
carbonate is therefore a contribution of the three which we call hybrid. If we write the hybrid structure
of carbonate ions, all the bonds will be one and one-half bonds, making all the bonds equal as illustrated
above.

Rules in Writing Resonance Structures

Lewis formulas are misleading in the sense that atoms and electrons are shown as being static. By being
essentially two-dimensional representations they also fail to give an accurate idea of the
three-dimensional features of the molecule, such as actual bond angles and topography of the molecular
frame.

Furthermore, a given compound can have several valid Lewis formulas. For example CO32- can be
represented by at least three different but valid Lewis structures called resonance forms, or resonance
structures, shown above. However, a stable compound such as the above does not exist in multiple
states represented by structures I, or II, or III. The compound exists in a single state called a hybrid of all
three structures.

When writing resonance structures keep in mind that THEY ALL MUST BE VALID LEWIS FORMULAS. The
factors that make up valid Lewis formulas are as follows.

1. Observe the rules of covalent bonding, including common patterns as discussed previously. Make sure
to show all single, double, and triple bonds.

2. Account for the total number of valence electrons being shared (from all the elements), including
bonding and nonbonding electrons. Make sure to show these nonbonding electrons.

3. Account for the net charge of the molecule or species, showing formal charges where they belong.

4. Observe the octet rule as much as possible, but also understand that there are instances where some
atoms may not fulfill this rule.

5. Avoid having unpaired electrons (single electrons with no partners) unless the total number of valence
electrons for all elements is an odd number. This is not a very frequent occurrence, but the following
example shows a species that could exist as a reaction intermediate in some high energy environments.
6. If the structure exists in several resonance structures, the most stable resonance structure is the one
that has no charges followed by less

Example: Write the Lewis structures of the following compounds and account if resonance structures
exist.

NH4+, C2H6, C2H4, C2H2, NO31-

or CH3-CH3 or CH2=CH2

Example: Write the Resonance structures of NO3-1.

1. Count up the valence electrons: (1*5) + (3*6) + 1(ion) = 24 electrons

2. Draw the bond connectivities:
3. Add octet electrons to the atoms bonded to the center atom:

4. Place any leftover electrons (24-24 = 0) on the center atom:

5. Does the central atom have an octet?

● NO, it has 6 electrons
● Add a multiple bond (first try a double bond) to see if the central atom can achieve an
octet:

6. Does the central atom have an octet?

● YES
● Are there possible resonance structures? YES
We would expect that the bond lengths in the NO−3NO3− ion to be somewhat shorter than a single
bond.

Hybridization and Molecular Geometry of Compounds

Lewis dot structures are very useful in determining the types of bonds in a molecule, but they may not
provide the best insight into the spatial geometry of a molecule, i.e., how the nuclei in a molecule are
arranged in space. The shape of molecules is very important in determining how they might react with
other molecules. For example in the Lewis structure of methane which is illustrated below,

does not project the correct orientation of atoms in space around the central atom. Looking at
the electronic configuration of C which is 1s2 2s2 2px1 2py12pzo, it needs only hydrogen to complete the
unpaired electron of carbon resulting in a possible compound which is CH2; however, CH2 is an unstable
compound. The basic explanation for this one is the excitation of electron in carbon, electron from the
lower energy 2s orbital transfers to the 2pz empty orbital; thus excited carbon will have an electronic
configuration, 1s2 2s1 2px 1 2py1 2pz1. This configuration now accounts for the formation of four bonds in
CH4. But then again, it doesn’t project the correct orientation of the hydrogen around the carbon atom.
The three p orbitals are orthogonal (90o to each other), so we expect that if the three 1s orbital of H will
combine with this three 2p orbitals a 90 o angle will be formed whereas the 2s1 will bond with 1s orbital
of H forming a 180 o angle. For a molecule to be stable, all orbitals should have similar energy and
charge distribution. The fact that these two expected angles were not observed in methane
experimentally, but rather a uniform 109.5o angle was observed in every H-C-H bond angle would
indicate that orbitals mix or hybridize to attain stability. The mixing of the s orbital of C with the three 2p
orbitals would result in a hybridized orbital which is classified as sp3, and all the unpaired electrons of
carbon with same energy and charge density can now interact with the s orbital of hydrogen with equal
orientation in space. Carbon can form three types of hybridization as illustrated below.
Oxygen can exhibit two types of hybridization, sp3 and sp2 whereas Nitrogen can exhibit three types of
hybridization, sp3, sp2, and sp. For central atoms with d orbitals, the most common type of
hybridizations are sp3d and sp3d2.

One way to explain the symmetric geometry of a molecule is with the VSEPR Principle—valence shell
electron pair repulsion. VSEPR says that electron pairs, either in bonds or as unshared electron pairs,
want to get as far away from each other as possible because of the electrostatic repulsion of the negative
electrical charges. The tetrahedral structure of methane optimizes the distance between electron pairs
resulting in a tetrahedral geometry with 109.5 o angle. Carbon will have 4 sp3 electrons, molecular
geometry which is described as tetrahedral, and a bond angle of 109.5o. If we are going to make a
general formula for this kind of hybridization wherein A represents the central atom and B represents
the surround atom and E represents the lone pair, then tetrahedral structure will fall in this formula, AB4

In the case of N in NH3, there are three bond pairs and one lone pair. VSEPR predicted that
repulsion of the lone pair with the bond pair electrons is greater than with 2 bond pair electrons
thus resulting into a pyramidal structure:

Electronic configuration of Nitrogen according to Hund’s Rule:

1s2 2s2 2px1, 2py1, 2pz1

Electronic configuration of sp3 N (mixing of 2s and 3p’s)

1s2 (2sp3)2 (2sp3)1 (2sp3)1 (2sp3)1

In the case of NH3, it will have a trigonal pyramidal description of its geometry due to the
presence of the lone pair and with a bond angle of 107.8 which is again closer to the angle of an
sp3 hybridized electron. In this case, N wil have 5 sp3 electrons: 3 from the bonding electrons
and 1 lone pair of electrons. The general formula for this molecule would be AB 3E

The oxygen in water is also sp3 hybridized with a molecular geometry described as bent or
V-shape and with a bond angle of 105 o. Water will fall within this formula, AB 2E2.

Electronic Configuration of Oxygen according to Hund’s Rule

1s2 2s2 2px2, 2py1, 2pz1

Electronic Configuration of sp3 O

1s2 (2sp3)2 (2sp3)2 (2sp3)1 (2sp3)1

Predicting hybridization and Molecular geometry in compounds with multiple bonds

Compounds with multiple bonds will be counted as one pair. For example in the structure of
ethene, each carbon is counted only as 3 bonds instead of 4, thus sp2 hybridized. In the case
of CO2, the number of bonds around C is counted as 2 instead of 4, thus sp hybridized.
Similarly in acetylene, each C is sp2 hybridized.
This is summarized in the table presented below.

Hybridization and Molecular Geometry of Compounds

A= central Atom; E= electron pair; B= bonding pairs

Class total no. of # of Bonding # of Hybridization Geometry Examples

e-Pairs e-Pairs lone pairs

AB2 2 2 0 sp linear BeCl2

AB3 3 3 0 sp2 trigonal planar BCl3

AB4 4 4 0 sp3 tetrahedral CH4, CCl4

AB3E 4 3 1 sp3 trigonal pyramidalNH3, PCl3

AB2E2 4 2 2 sp3 Bent H2O, H2S

Characteristics of Covalent Bond

1. Bond Polarity- when atoms in a bond have different electronegativities (ability of the atom to
pull electrons closer to its nucleus), electron density in a bond will not be equally shared, one
will have a lower density (indicated by a partial positive charge) and the other will have a higher
electron density (indicated by a partial negative charge). The polarity of the bond or a molecule
is measured in terms of dipole moment which is a vector quantity. The larger the difference in
electronegativity, the larger the dipole moment. The distance between the charge separation is
also a deciding factor into the size of the dipole moment. The dipole moment is a measure of the
polarity of the molecule. When two electrical charges, of opposite sign and equal magnitude,
are separated by a distance, an electric dipole is established. The size of a dipole is measured by
its dipole moment ( μ ). Dipole moment is measured in Debye units, which is equal to the
distance between the charges multiplied by the charge (1 Debye equals 3.34×10−30Cm ). The
dipole moment of a molecule can be calculated by Equation 1 :
Relative electronegativity of some elements:

The greater the difference in electronegativity, the more polar the bond.

For example: H-F is more polar than H-Cl because F is more electronegative than Cl. If the
electronegativity difference between the two atoms in a bond is relatively small, it is classified as a
nonpolar bond such as C-H in CH4. Polarity of a bond does not always lead to the polarity of the
molecule especially if there are more than one bond. For example H2O and NH3 are both polar
because there is a net dipole among bonds whereas CCl4; although the bond is polar the whole
molecule is nonpolar because the net dipole is equal to zero

Which of the following compounds is/are polar; is/are nonpolar

CO2, BF3, C2H2, Cl2CO, CHCl3, CH3OH

Answer: Polar molecules: Cl2CO, CHCl3 and CH3OH

Non-polar molecules: CO2, BF3, and C2H2

Another important properties of covalent bonds are bond strength and bond energy (the energy needed
to break the bond). Generally the greater the number of atoms that hold the two atoms together, the
stronger the bond; the more polar the bond,the stronger the bond. The number of bonds that hold the
two atoms together is what you call bond order. In methane the bond order between C-H is one; in
ethene the bond order between C=C is two; whereas in acetylene the bond order between C-C is three.

Arrange the following in increasing Bond energy:

C-O, C-C, C-N, C-F

Answer: C-C, C-N, C-O, C-F

Reason: increasing polarity

Arrange the following in increasing Bond strength

C=O, C=C, CN, C-C

Answer: C-C, C=N, C=O, CN

Reason: increasing bond polarity and bond order