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CHAPTER 8 & SECTION 12.3

Reading Assignment:

 8-1 Chemical Bond Formation

 8-2 Covalent Bonding and Lewis Structures
 8-3 Atom Formal Charges in Covalent Molecules and Ions
 8-4 Resonance
 8-5 Exceptions to the Octet Rule
 8-6 Molecular Shapes
 8-7 Bond Polarity and Electronegativity
 8-8 Bond and Molecular Polarity
 8-9 Bond Properties: Order, Length, and Energy
 12-3 Bonding in Ionic Compounds: Lattice Energy
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Chemical Bond Formation

Things we must consider:
 What holds the atoms in a molecule or ionic compound together?
 Why are atoms in molecules often distributed at strange angles?
 Why are molecules three dimensional?
 Can we predict the structure of a compound?
 How does structure relate to chemical and physical properties?

Bond Polarity and Electronegativity
 Electronegativity is a measure of the ability of a bonded atom to attract the
electrons in the bond from other atom(s) to which it is bonded.

 The electronegativity trend follows, in general, the electron affinity trend.

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Types of Chemical Bonds:

 Covalent - e– sharing from the outermost shell

 Ionic - e– transfer from the outermost shell

Na: [Ne] 3s1 Na+: [Ne]

Cl: [Ne] 3s23p5 Cl− : [Ar]

 Metallic - mobile valence e–

The Nature and Properties of Chemical Bonds Between Atoms

Ionic bond

Bond type
Non-polar covalent bond
Covalent bond
Polar covalent bond
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IONIC BOND

 Nature of the atoms forming the bond: this bond is formed between a metallic
and a nonmetallic element whose electronegativities differ widely.

 Usually, the difference in electronegativity is  1.7.

 Nature of the bond: there is an actual transfer of an electron or electrons from the
metal to the nonmetal. Electrostatic attractions hold the ions together. No
individual molecules exist. Ionic compounds are solids at room temperature and
their melting points and boiling points are high. In aqueous solutions or in the
melt, ionic compounds break up into ions and conduct electricity.

Examples

NaCl BaO CsF

change in electronegativity 2.1 2.6 3.3

m.p. (C) 801 1 918 703

NON-POLAR COVALENT BOND

 Nature of the atoms forming the bond: this bond is formed between nonmetallic
elements with the same electronegativities or electronegativities that differ by 0.5.

 Nature of the bond: there is an equal sharing of electron pairs. The bond is
described by using a dot formula, F : F , or as F F. Individual molecules exist.

Examples: H2, F2, Cl2, Br2, I2, N2, O2, P4, S8, NCl3, PH3, CH4, etc...

change in electronegativity is 0 to 0.5.

POLAR COVALENT BOND

 Nature of the atoms forming the bond: this bond is formed between elements,
usually nonmetals, whose electronegativities differ somewhat but not very widely.
An approximate rule of thumb is that the elecronegativity difference is between
0.5 and 1.5.
 Nature of the bond: there is an unequal sharing of electron pairs. The bond has
a negative end and a positive end.
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 For example, in HCl

(H  Cl), the Cl end is more negative than the H end. Individual molecules exist.
While the individual bonds may be polar, the entire molecule may be non-polar
due to overall symmetry (i.e. CO2, CCl4, etc.)

Examples: HCl, HBr, HF, H2O, NH3, CO2

change in electronegativity 0.9 0.7 1.9 1.4 0.9 1.0

CHEMICAL BOND
 The force that holds two atoms together
 Bonding occurs using valence electrons
 Electrons in an atom can be categorized as either valence or core electrons
 Atoms try to get 8 electrons in the valence
 Lewis symbols help us to track the valence electrons and predict bonds.

Lewis Structures (Diagrams) of covalent compounds and polyatomic ions show the
bonding arrangement of those compounds or ions.

Lewis structures are based on the idea of electron sharing between atoms in order to
complete an electron octet. They show a two-dimensional bonding picture of a
molecule or an ion.
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The valence electrons are represented as follows:

 non-bonded electron pairs: xx or 

(free or lone pairs)
Example:

 bonded electron pair(s): – (the dash represents two bonded electrons)

(shared between two atoms)

Example:
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Double and Triple Bonds

LEWIS STRUCTURES OF COVALENT COMPOUNDS AND POLYATOMIC IONS

A probable arrangement of the atoms can be deduced as follows:

 The structure assumed must be consistent with the known valences of the
elements: e.g. H forms one bond,
F forms one bond,
O forms two bonds,
N forms three bonds,
C forms four bonds, etc.

 In a molecule with the formula AXn the atom A is usually the central atom to which
X are attached:

e.g. CH4, BeH2, PCl5, SF6, etc.

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 Usually, the first step is to draw a diagram of the molecule or polyatomic ion,
showing the atoms connected by single bonds to the central atom.

e.g. CH4 H2O NH3

Then:
 Add the number of valence electrons of each atom in the molecule to find the
total number of valence electrons.

 Subtract the number of electrons needed to form the single bonds from the total
number of electrons.

 Use the remainder to complete octets around each atom except hydrogen.

Exceptions to the octet rule: compounds of Be and B have less than 8 electrons in their
valence shell. Be ends up with 4 electrons and B has 6 electrons.
The rule is that if there are insufficient electrons to complete all the octets, complete those
of the more electronegative atoms first.

e.g. BeCl2 BH3

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Coordinate covalent bond:

 A covalent bond is formed by two atoms sharing a pair of electrons. The atoms
are held together because the electron pair is attracted by both of the nuclei.
 In the formation of a simple covalent bond, each atom supplies one electron to
the bond - but that doesn't have to be the case.
 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.

If the molecule is charged, that is, if it is a polyatomic ion - add one electron for each
negative charge or subtract one electron for each positive charge.

e.g. H3O+ NH2 –

Atoms from the 3rd or later period:

 If the central atom is from period 3 or a later period, the octet rule may not apply.
These atoms can have more than 8 electrons in their valence shell (hypervalent):

e.g. PCl5 SF6

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 If there are more than enough electrons to complete all octets, add the remaining
electrons in pairs to the central atom (which must be from the 3rd or a later period).

e.g. SCl4 BrF4+ SbCl52–

Double or triple bonds:

If atoms of N, O, C, and S still have an incomplete octet, convert nonbonding electron

pairs to bonding electron pairs. (Use nonbonding pairs to form double or triple bonds
until each atom has an octet.)

e.g. O2 C2H4 CN –
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Resonance
 In writing resonance structures, only electrons are shifted around, not atoms.
Species having resonance are built up of one type of molecule whose structure is
assumed to be in between (a hybrid of) those resonance structures.

 Species having resonance experience special stability. This is due to the

delocalization of the electrons.

Examples

C6H6:
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O3:

CO32- :

Atom Formal Charges in Covalent Molecules and Ions

 Formal charge can be assigned to any atom of a given Lewis structure. When
calculating a formal charge, we are essentially comparing the number of electrons
before and after bonding.

 Formal charge can be calculated using the following formula:

NVE: number of valence electrons for the atom

LPE: number of lone electrons on an atom
BE: number of bonding electrons around the atom

The following rules are helpful:

 For neutral molecules, the sum of the formal charges must add up to zero.
 For cations, the sum of the formal charges must equal the positive charge.
 For anions, the sum of formal charges must equal the negative charge.
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 When several Lewis structures are possible, the most stable structure will be when
 the atoms have the smallest amount of formal charge
 any negative charge resides on the more electronegative atom

Examples:

CO2

OCN−

Molecules with Odd Number of Electrons:

Free radical: chemical species with an unpaired electron and very reactive
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Molecular Shapes

Valence Shell Electron Pair Repulsion (VSEPR) Theory

 Lewis structures tell us how atoms are connected in a molecule: bonds (bp) & lone
pairs (lp) etc…
 The 3–D shape of a molecule is however, determined by its bond angles.

 The shape of molecules depends on the number of electron pairs around the central
atom. Electron pairs repel each other and will adopt a position in space to be so far
apart as possible and thereby minimise the repulsion between them.

 The number of electron pairs around the central atom(s) is called the repulsion
number or the number of regions of high electron density. Correct Lewis structures
are important.

 Table 1 shows the geometry of some simple molecules (or ions) in which the central
atom has no lone pairs.

Examples are: BeCl2, BF3, CH4, NH4+, PCl5, and SF6.

 Table 2 shows the geometry of simple molecules and ions in which the central atom
has one or more lone pairs. Since the lone pairs exert a larger repulsive effect than
do bonded pairs (they take up more space than a bonded pair) the bond angle will
slightly decrease for the bonded pairs:

e.g. series of CH4, NH4+, NH3, H2O.

Axial versus Equatorial positions

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Table 1: Geometry of some simple molecules and ions: the central atom has no lone pairs.

Molecule Example: Number of Electron pair Molecular

type: electron pairs: geometry geometry
(rep. #)

AB2 BeCl2

AB3 BF3

AB4 CH4

AB5 PCl5

AB6 SF6
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Table 2: Geometry of some simple molecules and ions: the central atom has one or more
lone pairs.

Molecule Example # of # of # of Electron pair Molecular

type electron lone bonding Geometry geometry
pairs pairs pairs
(rep. #)

AB4 CH4

AB3E NH3

AB2E2 H2O
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Molecule Example # of # of lone # of Electron Molecular

type electron pairs bonding pair geometry
pairs pairs Geometry
(rep. #)

AB4E SF4

AB3E2 ClF3

AB2E3 XeF2
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Molecule Example # of # of lone # of Electron Molecular

type electron pairs bonding pair geometry
pairs pairs Geometry
(rep. #)

AB5E BrF5

AB4E2 XeF4
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Multiple Bonds and Molecular Geometry

 Electrons in a double or a triple bond occupy the same region of space and are
counted as one region of high electron density.
 For the repulsion purposes, they count essentially as one pair.
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POLARITY OF MOLECULES

 Many molecules are polar, that is, one end of the molecule has a small net positive
charge, while the other end has a small net negative charge.

 Once the overall geometry is known, the polarity of a molecule or ion can be deduced.
The dipole moment of a molecule or ion is the resultant of the individual bond dipoles.
Each bond dipole can be considered a vector, represented by an arrow that points
from the positive to the negative end.

 The net dipole moment of the molecule is then obtained by the addition of all vectors.
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Isomers: compounds with the same molecular formula but different structure.
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Bond Properties: Order, Length, and Energy

Covalent bond strength increases with increasing electronegativity difference between

atoms.

example: HCl bond is stronger than the HBr bond

Bond Length and Bond Order

 Bond length is the distance between the nuclei of two bonded atoms.

 It depends on the type of a bond: single bonds are the longest and triple bonds are
the shortest.

 Bond length is related to atom sizes.

 Bond order (b.o.) can be pictured as the number of covalent bonds between
bonded atoms.
 In resonance structures, fractions are possible.
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Examples:

C2H6 C2H4 C2H2

C-C b.o.: _______ _______ _______

carbon-carbon
bond length 154 134 121
(pm)

 Covalent bond strength increases with increasing bond order.

example: C=C bond in stronger than C–C bond

triple > double > single

Bond Order: 3 2 1

 Bond length decreases with increasing bond order (Strength)

example: C=C bond is shorter than C–C bond

other examples
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Bond Dissociation Enthalpy

 Bond enthalpy is the energy required to break a bond in a mole of gaseous

substance.

Cl–Cl(g)  2Cl(g) H = D(Cl–Cl) = 242 kJ

 Bond enthalpies are always positive.

 energy is always required to break a bond

H is always positive for bond breakage

 energy always released when a bond forms

H is always negative for bond formation

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 Tabulated bond enthalpy values are averages.
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Hreaction= H (bonds broken) – H (bonds formed)

Exercise

Estimate the enthalpy change for the following reaction:

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SECTION 12-3 Bonding in Ionic Compounds: Lattice Energy

Lattice energy, ∆latticeU: energy of formation of one mole of a solid crystalline ionic
compound when ions in the gas phase combine
Example:
Na + (g) + Cl− (g) → NaCl (s)

 Ionic compounds have very high

melting points.

 Indication of the strength of the

bonding in an ionic crystal.

C is a constant

d: is the distance between the ion

centers

e is the charge on an electron

n+ is the number of positive charges on

the cation

n- is the number of negative charges on

the anion.

 Typically use lattice enthalpy: ΔlatticeH

 It is difficult in estimating energy quantities.

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Born Haber cycle helps explain this

Note: Appendix L and F are found in your textbook .