UNIT 2

Chemical Bonding and Structure

• Bonding: is the joining of at least two atoms to form a molecule or compound. The electrons in the
valence shell are the active portion of an atom during bonding.

• A chemical bond is a mutual electrical attraction between the nuclei and valence electrons of
different atoms that binds the atoms together.
Where, A= attraction force, R= repulsion force Chemical bond is formed when A>R:

Example: H + H→ H2 (g) but, He + He → no reaction since R>A.

• Why atoms combined to form compounds, clusters, molecules/ polyatomic ions?

➢ To attain octet (eight) rules

➢ To have lower energy (to be stable)
TYPES OF CHEMICAL BONDING

• When atoms bond, their valence electrons are redistributed in ways that make the atoms
more stable. The way in which the electrons are redistributed determines the type of
bonding.
• There are different types of chemical bonds that results by transfer or sharing of electrons.
These are:
➢ Ionic bond = Electropositive element + Electronegative elements
Na + Cl → NaCl
➢ Covalent bond = Electronegative element + Electronegative elements
F+F → F 2
 ➢ Metallic bond = Electropositive element + Electropositive element
Li+Li →Li

Elements can be classified as:

➢ Electropositive elements, whose atoms give up one or more electrons

➢ Electronegative element which take up electrons
➢ Elements which neither tends to lose or gain electrons

Ionic Bond/Electrovalence bond

• Ionic bond is a type of chemical bond that results from the electrostatic force of attraction between
two oppositely charged ions.
• In general, an ionic bond is formed between two atoms that contain greater electronegativity
difference and it is between a metal atom and a nonmetal atom. Example: NaCl, LiF, MgCl2.
➢ Favorable Condition For Ionic Bond Formation

o Low ionization energy of the metals

o High electro-affinity of the nonmetals

o High lattice energy

o High electro-negativity difference between a metal and a nonmetal atom

Note! Ionic compounds are usually formed when metal cations bond with non-metal anions.
• Example: Sodium atom lose its valence shell electron and form sodium ion (Na+) while chlorine
accept one electron to attain octet, and form chloride ion (Cl-).

• The electrostatic force of attraction between sodium ion and chloride ion is known as ionic bond.

• Notice that when sodium loses its one valence electron it gets smaller in size, while chlorine grows
larger when it gains an additional valence electron.

• Positive ions tend to be smaller than their parent atoms while negative ions tend to be larger than
their parent.
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 Properties of ionic compounds

• They are solids with high melting points (> 400°C) due to strong attraction of force between ions.

• Many are soluble in polar solvents such as water. Most are insoluble in nonpolar solvents, such as

hexane, C6H14, and carbon tetrachloride, CCl4.

• Molten compounds conduct electricity well because they contain mobile charged particles (ions)

• Aqueous solutions conduct electricity well because they contain mobile charged particles (ions).

• They are often formed between two elements with quite different electronegativities,

usually a metal and a non-metal.

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 Explain factors that affect the strength of ionic bond

• Size of the cation and anion; ionic bonds are stronger when the size of the cation is small e.g. is

LiCl more ionic than NaCl.

• Electronegativity/electropositivity differences; the bigger the difference of these factors

between the reacting elements, the stronger the ionic bond e.g. NaCl is more ionic than NaI.

• Charges on the ions. The bigger the charges on ions the stronger the ionic bond e.g. the ionic

bonds of CaO are stronger than those of NaCl.

 Covalent Bond
• Covalent bond is formed between two atoms due to the sharing of electron pair(s). It is formed
between two atoms that contain the same or small difference in electronegativity.

• Based on the number of shared electron pairs covalent bond, divided as single, double, and triple
bonds.

• There are different types of covalent bonds like polar and non-polar and coordinate covalent
bonds.
➢ Polar-Covalent Bond is a covalent bond in which the bonded atoms have an unequal attraction
for the shared electrons.
Example: hydrogen-chlorine bond (H δ+- Clδ⁻ ).
• Polar covalent bonding occurs because one atom has a stronger affinity for electrons than the
other. When electrons are shared but shared unequally.
2. Non-polar covalent bond is a covalent bond in which the bonding electrons are shared equally by

the bonded atoms, resulting in a balanced distribution of electrical charge (no net dipole moment).

• Here are some examples of nonpolar covalent bonds:

Example; hydrogen-hydrogen bond (H: H), O2 , N2, Cl2. The electrons are shared equally.
3. Coordinate Covalent bond: A coordinate covalent bond (also called a dative bond) is
formed when one atom donates both of the electrons to form a single covalent bond. These
electrons originate from the donor atom as an unshared pair.

Example
 Properties of covalent compounds

• They are gases, liquids, or solids with low melting points (typically 300 °C).

• Many are insoluble in polar solvents

• Most are soluble in nonpolar solvents, such as hexane, C6H14, and carbon tetrachloride, CCl4

• Liquid and molten compounds do not conduct electricity

• Aqueous solutions are usually poor, conductors of electricity because most do not contain charged

particles

• They are often formed between two elements with similar electronegativities, usually non-metals
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Exercise 1
1. Explain the formation of bonds in the following pairs of elements: a) potassium and chlorine, b)
magnesium and oxygen and c) sodium and oxygen.
2. Which of the following elements will form a ionic bond with chlorine and why? Calcium, Carbon,
Oxygen and Silicon.
3. Which of the following compounds contain both ionic and covalent bonds?
a CO2 c Na2CO3 b Cl2O d BaCl2
4. Of the following, the most polar bond is:
a P – Cl cS–O b Si – F dC–N
5. Classify the given molecules as polar or non-polar:
d H2S b NF3 e CCl4 c PCl3 f CO2
 Lewis Structure

• Lewis structure is a simple model of chemical bonding using diagrams that represent bonds between
atoms as lines or pairs of electrons as dots.

• A Lewis structure shows each atom in the molecule or ion and its relationship to the other atoms. It
also shows all bonding electrons as well as those valence electrons that are nonbonding.

• During drawing of Lewis structure all atoms should obey octet rule.

➢Octet rule states that atoms lose, gain, or share electrons in order to have a full valence shell of
eight (8) electrons. (Hydrogen is excluded because it can hold a maximum of two electrons in its
valence shell).

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Steps in writing Lewis structure

1) Calculate the total number of valance electrons for molecules by adding the number of valance

electrons for each species that participate in the formation of molecules/compounds.

2) Determine the number of electron pairs by dividing the total number of valance electrons by two

to get number of paired electrons.

3) Predict the central atoms: Place the least electronegative element at the center, except for H

which is always an outer atom.

4) Distribute the remaining electrons to the attached atoms till they acquired octet rules.

5) If there are still remaining electrons distribute them as lone pairs to the central atom.

6) If octet rules not obeyed for the central atom, it forms multiple bonds.
1) Draw the Lewis Structures for:
a) NH3 b) CO2 C) CHO2−

a) NH3 Valence e- = 5 + 3 = 8 e-

# of bonding pairs = 𝟖
= 4 pairs
𝟐

Draw single bonds between terminal atoms & central atom:

..
H–N–H
H N H H
H
Find the # of lone pairs: 4 pairs – 3 pairs used = 1 lone pair

This lone pair is on the central atom (H cannot have any more)
b) CO2 Valence e- = 4 + 12 = 16 e-
𝟏𝟔 = 8 pairs
# of bonding pairs =
𝟐
Draw single bonds between terminal atoms & central atom:

O C O
Find the # of lone pairs: 8 pairs – 2 pairs used = 6 lone pairs
Add three lone pairs to each oxygen (terminal atoms):

O–C–O O–C–O
Lone pairs available – lone pairs used = 6 – 6 = 0
(No e- pairs remain for C atom)
But C does not have an octet, one lone pair of e- from
each oxygen must be used to form a double covalent
bond with carbon:
 C) CHO2−
Valence e- = 4+1+ 2(6) + 1e = 18 valence electrons

𝟏𝟖
# of bonding pairs = 𝟐
=9

Draw a skeleton structure of the ion :

Distribute the remaining electrons as lone pairs on the terminal atoms:

Rearrange the electrons of the outer atoms to make

multiple bonds with the central atom in order to obtain
octets wherever possible.
Exercise 2

1. Draw the Lewis structure for the given molecules and state whether the

molecule is polar or non-polar:

a PF–4

b ICl–4

c N2F2
 Resonance Structures
• Resonance is a condition occurring when more than one valid Lewis structure can be written for a
particular molecule due to the presence of multiple bonds.

• The structure of the same relative placement of atoms but different locations of bonding and non-
bonding electron pairs.

• Systems which have more than one Lewis structure are Resonance Structures.

• Resonance is delocalization of electrons through double bond. NO3- is a classic example of

resonance.
 Formal Charge
➢ The theoretical charge on an atom in the molecules. It helps to check whether the Lewis structure is
stable or not.
➢ The smallest formal charge is the more stable in Lewis structure regardless numerical sign.

➢ FC = formal charge; #Ve. = Number of valence electrons

➢ #BE = bonding electrons; #LPE = lone pair electrons
➢ Example: NCO- has three possible resonance forms
• A few guidelines involving formal charge can be helpful in deciding which of the possible
structures is most likely for a particular molecule or ion:

1. A molecular structure in which all formal charges are zero is preferable to one in which some

formal charges are not zero.

2. If the Lewis structure must have nonzero formal charges, the arrangement with the smallest

nonzero formal charges is preferable

3. Lewis structures are preferable when adjacent formal charges are zero or of the opposite sign

4. When we choose among several Lewis structures with similar distributions of formal charges, the

structure with the negative formal charges on the more electronegative atoms is preferable

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Examples:1. The thiocyanate ion could have three different molecular structures: NCS–, CNS–, or
CSN–

• Possible Lewis structures and the formal charges for each of three possible structures are:

• Note that the sum of formal charges in each case is equal to charge of ion (–1).

• However, the first arrangement of atoms is preferred because it has the lowest number of atoms with
nonzero formal charges.

• Also, it places the least electronegative atom in the center, and the negative charge on the more
electronegative element.
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Examples: 2. Which is the most likely molecular structure for nitrite (NO2−) ion? Possible Lewis
structures and the formal charges for each possible structures are:

-1 +1 -1 0 0 -1

• Note that the sum of formal charges in each case is equal to charge of ion (–1).

• However, the second arrangement of atoms is preferred because it has the lowest number of atoms
with nonzero formal charges.

• Also, it places the least electronegative atom in the center, and the negative charge on the more
electronegative element.
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Limitations of the Lewis dot structure

As handy as the Lewis dot structure is, it has its limitations. We've already touched on a few
of them. Here are some more:

➢ It doesn't show the length of bonds or the size of atoms.

➢ It doesn't show the different types of orbitals.

➢ It doesn't accurately represent resonance.

➢ It doesn't show geometry.

➢ does not predict the correct magnetic behavior of molecules

➢ It assumes that all atoms follow the octet rule.

Exceptions to the Octet Rule:

❑ Many covalent molecules have central atoms that do not have eight electrons in their Lewis
structures. These molecules fall into three categories:

❑ Electron-deficient molecules

❑ Odd-electron molecules

❑ Expanded Valence Shells (Hypervalent molecules)

a) Electron-Deficient Molecules: gaseous molecules containing either Be or B as the central atom;
have fewer than 8 electrons around the Be or B (4 e- around Be and 6 e- around B) (BF3).

b) Odd-Electron Molecules: have an odd number of valence electrons; examples include free
radicals, which contain a lone (unpaired) electron and are paramagnetic (use formal charges to
locate the lone electron) (NO2). Example: CH3, OH, H, NO2 etc.

c) Expanded Valence Shells: for molecules that have more than 8 electrons around the central atom;
use empty outer d orbitals; occurs only with a central atom from Period 3 or higher (SF6, PCl5).
E.g. : PCl5, SF6, H2SO4, H3PO4
 Valence shell electron-pair repulsion theory (VSEPR theory)

• VSEPR theory support us to predict the molecular structure, including approximate bond angles around
a central atom, of a molecule from an examination of the number of bonds and lone electron pairs in its
Lewis structure.

• It assumes that electron pairs in the valence shell of a central atom will take an arrangement that
minimizes repulsions between these electron pairs by maximizing the distance between them.

• Bond pair is pair of electrons which participate in chemical bond.

• Lone pair is pair of electrons which don’t participate in chemical bond.

• Geometry (Electron-pair Geometry) is determined by both the bond pair and lone pair of electrons.

• Shape (Molecular Structure) is determined only by the bond pair of electrons.

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 The Main Points Of VSEPR Theory
• Electron pairs repel each other and tends to stay away
Lone pair-lone pair, lone pair-bonding pair and bonding pair-bonding pair
• Different electron pairs have different types of repulsion
Lone pair-lone pair > lone pair-bonding pair > bonding pair-bonding pair
• Geometry and shapes is determined by bond pairs and lone pairs
• If the lone pair is zero geometry = shape (Molecular Structure)
• If lone pair is not zero geometry are different from shapes
• A lone pair of electrons occupies a larger region of space than the electrons in a triple bond; in turn,
electrons in a triple bond occupy more space than those in a double bond, and so on. The order of
sizes from largest to smallest is:
Lone pair > triple bond > double bond > single bond
 Electron-pair Geometry versus Molecular Structure

• It is important to note that electron-pair geometry around a central atom is not the same thing as its
molecular structure.
• Molecular structure describes the location of the atoms, not the electrons.
• We differentiate between these two situations by naming the geometry that includes all electron
pairs the electron-pair geometry.
• The structure that includes only the placement of the atoms in the molecule is called the molecular
structure.
• The electron-pair geometries will be the same as the molecular structures when there are no lone
electron pairs around the central atom, but they will be different when there are lone pairs present
on the central atom.
• Example water (H2O) molecule the geometry of water molecule is tetrahedral and the shape bent
• For example, the methane molecule,, which is the major component of natural gas, has four bonding pairs of
electrons around the central carbon atom; the electron-pair geometry is tetrahedral, as is the molecular
structure
• On the other hand, the ammonia molecule, NH3, also has four electron pairs associated with the nitrogen
atom, and thus has tetrahedral electron-pair geometry.

The following procedure uses VSEPR theory to determine the electron pair geometries and the
molecular structures:
1. Write the Lewis structure of the molecule or polyatomic ion.
2. Count the number of regions of electron density (lone pairs and bonds) around the central atom. A single,
double, or triple bond counts as one region of electron density.
3. Identify the electron-pair geometry based on the number of regions of electron density: linear, trigonal
planar, tetrahedral, trigonal bipyramidal, or octahedral.
4. Use the number of lone pairs to determine the molecular structure. If more than one arrangement of lone
pairs and chemical bonds is possible, choose the one that will minimize repulsions
Example 1: Predicting Electron-pair Geometry and Molecular Structure: CO2 and BCl3 Predict the
electron-pair geometry and molecular structure for each of the following:
Difference Between Intermolecular
And Intramolecular Forces
 Molecular Structure And Dipole Moment
• Polar covalent bonds connect two atoms with differing electronegativity, 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:

• Dipole vectors are shown as arrows pointing along the bond from the less electronegative atom toward the
more electronegative atom.
• The trans isomer has no dipole moment (µ= 0 D) because the C – Cl bond polarities
balance each other. In contrast, the cis-isomer is polar (µ = 1.90 D) because the bond
dipoles partially reinforce each other, with the molecular dipole pointing between the Cl
atoms
 Dipole-Dipole forces
• Dipole-Dipole forces: When polar molecules are brought near one another, their partial charges act
as tiny electric fields that orient them and give rise to dipole-dipole forces; the partially positive end
of one molecule attracts the partially negative end of another.
• For compounds of approximately the same mass and size, greater is the dipole moment, greater is
the dipole-dipole forces between their molecules, so greater is the energy required to separate their
particles.
• For instance, both methyl chloride (CH3Cl) and ethanol (CH3CHO) have comparable mass and size,
but CH3Cl has a smaller dipole moment than CH3CHO; therefore, less energy is needed to
overcome the dipole-dipole forces between its molecules and it boils at a lower temperature.
• Dipole-dipole forces give polar cis-1,2-dichloroethene a higher boiling point than nonpolar trans-1,
2- dichloroethene.
• Dipole-dipole interaction occurs among the polar molecules due to the permanent dipoles of a
polar molecule. In a polar molecule, the positive pole of one molecule is attracted by the negative
pole of the other molecule.
 Hydrogen Bonding
• Hydrogen bonding is a special type of dipole-dipole forces that arise between molecules that
have a hydrogen atom bound to a smaller sized, most electronegative atoms. These atoms are:
Fluorine, Oxygen and Nitrogen
• The partially positive (δ+) H of one molecule is attracted to the partially negative (δ–) lone pair on
the F, O or N of the same or another molecule. As a result, hydrogen bonds result.
Example: In the molecule of ammonia, NH3,NH3, the N atom is highly electronegative and acquires
a partial negative charge due to the pulling of the shared pair. Therefore, in NH3,NH3, the H atom
possesses a partial positive charge. Due to the presence of partial positive and negative charges,
several molecules of NH3NH3 linked together through hydrogen bonds.
 London Dispersion Forces

• Dispersion or London Forces: Intermolecular forces in which non-polar atoms or molecules interact
by inducing dipoles in each other are known as dispersion or London Forces.
• These classes of intermolecular forces cause substances like CO2, Cl2, noble gases, etc., to condense
and solidify.
• Dispersion forces are very weak and are caused by a unexpected shift of electron density to one side
of the nucleus than the other
Factors Affecting Dispersion Forces

1. Number of electrons in an atom (more electrons, more dispersion force)

2. Size of atom or molecule/molecular weight

3. Shape of molecules with similar masses (more compact, less dispersion force).

4. The shape of the molecule affects the dispersion forces: long, thin molecules (like n-pentane tend

to have stronger dispersion forces than short, round ones (like neopentane). This is due to the

increased surface area in n-pentane.

Metallic Bond
• It is the attraction between metal atoms in a metallic crystal. It is formed between
electropositive metal atoms of same or different elements.

• Electrons in metals are said to be delocalized (not found in one specific region, such as
between two particular atoms).

• Delocalization can be used to explain conductivity, malleability, and ductility.

• In general, the greater the number of electrons per atom that participate in metallic bond
the stronger the metallic bond.

• E.g. the metal atoms Na, Cu, Ag, and Fe etc. are bound to each other in their crystals by
metallic bonds.
 CHEMICAL BONDING THEORIES
Valence Bond Theory (VBT)

• The basic principle of valence bond theory is that a covalent bond forms when orbitals of two atoms
overlap and the overlap region, which is between the nuclei, is occupied by a pair of electrons
• In the HCl bond, for example, the 1s orbital of hydrogen overlaps the half-filled 3p orbital of Cl
along the axis of that orbital. Similarly, in the Cl–Cl bond of Cl2, the two 3p orbitals interact end-to-
end, that is along the orbital axes, to attain maximum overlap.
The overlap may take place in two ways:

i. The half-filled p orbitals along the line joining the two nuclei. This is called as head on, end-to end,

end on or linear overlap and

ii. The half-filled p orbitals overlap along the line perpendicular to the nuclear axis. This overlapping

of p orbitals is parallel to each other, hence is called lateral or sideways overlapping.

iii. The extent of overlap influences bond strength.

 Overlap of Atomic Orbitals (Sigma and Pi Bonds)

Sigma σ bond:

• This type of covalent bond is formed by the end-to-end (head-on) overlap of bonding orbitals
along the internuclear axis.

• This is called head-on overlap or axial overlap.

• The sigma bond can be formed by the combination of atomic orbitals such as s-s overlapping,
s-p overlapping as well as p-p overlapping.

• The s-s overlapping is shown below:

1. s-s overlap in which half-filled s orbitals overlap,

2. s-p overlap where half-filled s orbital of one atom overlaps with one of the p orbital having one
electron only,

3. p-p overlap in which two half-filled p orbitals overlap.

Pi π bond:

• In the formation of π bond, the atomic orbitals overlap in such a way that their axes remain
parallel to each other and perpendicular to the internuclear axis.

• The orbitals formed due to sidewise overlapping consist of two saucer-type charged clouds above
and below the plane of the participating atoms.
 Hybridization of Orbitals

➢ The combination of atomic orbital is called hybridization

➢ The word ‘hybridization’ means ‘mixing
➢ Hybrid orbitals may be formed by mixing the characters of atomic orbitals that are close in energy
➢ The number of bond formed by an atom is the same as the number of unpaired electron that
combined in ground state.
sp hybrid orbitals

• Combination (mixing) of one s and one p orbital is called sp hybridization and the resultant orbitals
are called sp hybrid orbitals.
• VB theory explains this by proposing that mixing two non-equivalent orbitals of a central atom one s
and one p, gives rise to two equivalent sp hybrid orbitals that lie 180° apart.

Example: In the triatomic molecule BeCl2 the 2s and one of the 2p orbitals of the Be atom are
hybridized into sp hybrid orbitals. The remaining two 2p orbitals are left hybridized and unoccupied in
the orbital diagram.
sp2 hybrid orbitals

Example in BCl3, the boron atom has four orbitals but only three electrons in its valence shell. In most
boron compounds the hybridization scheme combines one 2s and two 2p orbitals into three sp2 hybrid
orbitals.
sp3 hybridization

• Carbon, the central atom in a molecule of methane CH4 has only two unpaired electrons in the
ground state. rule. Carbon in its excited state can form four bonds.
• The one 2s and three 2p-orbitals of carbon are mixed to produce four new orbitals that are equivalent
to each other in energy and in shape, but pointing in different directions,
• We might also expect to use sp3 hybridization not only for structures of the type AX4 type (as in
CH4), but also for AX3E type (as in NH3) and AX2E2 type (as in H2O).
sp3d hybridization
• PCl5, the central atom phosphorus has only three unpaired electrons in its ground state.
• Electrons must be unpaired to provide the correct number of unpaired electrons for bond formation
sp3d2 Hybridization
• Another structure featuring an expanded octet is SF6. Here, six hybrid orbitals are required
in order to describe bonding.
 Molecular Orbital Theory
• The Molecular Orbital Theory (often abbreviated to MOT) is a theory on chemical bonding
developed at the beginning of the twentieth century by F. Hund and R. S. Mulliken to describe the
structure and properties of different molecules.

• The molecular orbital theory states that each atom tends to combine together and form molecular
orbitals

The key features of the molecular orbital theory are listed below.

• The total number of molecular orbitals formed will always be equal to the total number of atomic
orbitals existing by the bonding species.

• There exist different types of molecular orbitals viz; bonding molecular orbitals, anti-bonding
molecular orbitals, and non-bonding molecular orbitals.
• Anti-bonding molecular orbitals will always have higher energy than the parent orbitals whereas
bonding molecular orbitals will always have lower energy than the parent orbitals.
• The electrons are filled into molecular orbitals in the increasing order of orbital energy (from the
orbital with the lowest energy to the orbital with the highest energy).
• The most effective combinations of atomic orbitals (for the formation of molecular orbitals) occur
when the combining atomic orbitals have similar energies.

Electron configuration in MO is given by:

 Bond Order
• Bond Order The term bond order is used to indicate whether a covalent bond is single (bond order =
1), double (bond order = 2) or triple (bond order = 3).

• Bond order is also an index of bond strength and is also used extensively in valence bond theory.
Generally, the higher the bond order, the stronger the bond (stable).

• The existence of molecules determined by bond order which is given by:

Bond Order = (1/2)*(Number of Bonding Electrons-Number of Antibonding Electrons)

Eg. In O2 10-6/2 = 2 , the molecule can exist

• A molecule exists only if the bond order is positive.
• If bond order is zero or negative, the molecule does not exist.
 Magnetic Properties
• A species with unpaired electrons exhibits paramagnetic property. The species is attracted by an
external magnetic field.
• A species in which all the electrons are paired, exhibits diamagnetism. Such species are not
attracted (and, in fact, are slightly repelled) by a magnetic field.
CRYSTALS
TYPES OF CRYSTALS
Exercise 1

1. Use the molecular orbital theory and derive the electron configuration of the following molecules.

Identify those which exist and do not exist.

a He2 b Be2 c B2 d C2 e N2

2. Draw a molecular orbital energy diagrams for:

a. C2– b. C2 c. C2+