UNIT 4

Objectives of Unit 4
 Draw Lewis structure of simple molecules and ions
 Describe the physical properties of formed compounds
 Use VSEPR theory to predict electronic and molecular geometry of simple molecules and
ions
 Explain the concept of hybridization
 Identify hybridization in simple molecules and ions
 Explain resonance and give examples in simple molecules

Electronic Structure and Chemical Bonding

a) What is a chemical bond?
b) What forces hold atoms together in a structure
c) How do these forces affect the structure of the compound

ATOMS are the smallest particles that take part in a chemical bond. In the structure of an atom; it
is electrons that participate in formation of a bond. The mode the atom will use to form a bond will
depend on its valence shell electron configuration.
A bond is a linkage between a pair of atoms. A bond may be described as:
i) Strong or weak
ii) Long or short
iii) Polar or non polar
iv) Single, double or triple.

There are 3 major types of bonds;

a) Ionic
b) Covalent/dative(coordinate
c) Metallic
And there are some intermolecular forces/associations that reinforce especially covalent bonds
i) Van der Waals
ii) Hydrogen bonds
iii) London forces
iv) Debye forces
v) Keesom forces.
There are no compounds or molecules that exhibit purely ionic, covalent or metallic bonds.

Why do atoms combine?

To attain chemical stability manifested as lack of reactivity; like in noble gases. The most stable
electronic arrangement is the noble gas configuration in which atoms have acquired their lowest
energy value. Therefore atoms react to achieve this stable electron configuration.

IONIC BOND
This linkage occurs in cpds that have a collection of ions(Mn+, Xn-) held together by electrostatic
forces of attraction. The ions arise from transference of an electron or electrons in order to achieve
stable noble gas configuration.
Ionic/electrovalent bond is usually formed between atoms that have significantly different
electronegativities. In such molecules the common electron pair can be fully displaced to more
electronegative atom leading to formation of a cation and an anion.
+ -
Na + Cl Na Cl
Each ion in the product has a noble gas configuration.
Molecules with ionic bonds are rear unless in gaseous state.

STRUCTURE OF IONIC COMPOUNDS/SOLIDS

Normally many ions cluster together in definite arrangements of crystal units forming a crystal.
Crystal lattice/structure is the commulative force that hold the crystal units together. The number
of ions that surround the central ion is known as coordination number(CN).
Generally ionic bonds are nondirectional ie isotropic(having same value in all directions). The
properties of most of these compounds are governed by polarization of of constituent ions.
Polarization
Is the relative displacement of the nucleus and the electrons of the outer electron shell surrounding
it under influence of the electric field of the adjacent, oppositely charged ion. The extend of the
polarization determines the extent of the ionic character and by extension its properties

Polarizability
is the ability of an ion to deform under the action of an external electric field. The ease of
deformation by the electric field increase with ionic size
F- < Cl- < Br- < I- : check against Li+
Li+ <Na+ <K+ <Rb+ <Cs+: check against F-

Polarizing power
Is the ability to deform or polarize another ion. It increases with decrease in ionic radius and with
increase in ionic charge.

AlI3 as compared to NaI

CHARACTERISTICS OF IONIC COMPOUNDS

1. Most simple ionic cpds tend to form hard and brittle solids due to GIS that arise from the strong
ionic bonds. The brittleness is because of the fact that crystal units break through their faultlines.
2.They usually have high mpt and bpts. Mpt and bpts are measures of thermal stability of a
compound. Since the solid is formed from many crystal units the total amount of heat required to
break them into liquid is large.
3.They conduct electricity in molten state. The cations and anions are delocalized in the liquid
state hence will migrate to the respective electrodes as charge carriers.
4.Most of them dissolve in high polarity solvents like water to form electric conducting solutions
NaCl(s) + H2O(l) Na+(aq) + Cl-(aq)
When the acqueous solution is diluted to infinity, the ions migrate to the electrodes conducting
electricity.

The ionic character of ionic cpds can be explained by FAJAN’S rules.

1.Covalent character in ionic cpds increase with;
i. Decreasing cation size and
ii. Increasing cation charge.
𝑞
A high charge density (𝑟 ) of small highly charged cations exert powerful polarizing effects that
distort the electron cloud around the anion

NaCl ----mpt 800°C while CaCl2 ------mpt 772°C charge effect, more covalent
KI ------mpt 686°C while LiI ------ mpt 449°C small size , more covalent

2.Covalent character increases with an increase in anion charge or anion size. Elns in larger more
negatively charged anions are more loosely held because of stronger shielding from the nuclear
charge. These anions are easily polarized.

LiBr-----mpt 552°C while Li3P ---sublimes higher charge.

LiF-----mpt 845°C while LiI-------------449°C large inion size

3.Covalent character is greater for cations with a non-noble gas EC ie 18 eln a pseudo-noble gas
EC. This affects mostly transition metals in which the d- electrons effectively shield the outer elns;
Ag+, Cu2+, Zn2+, Cd2+, Hg2+, Tl+ etc

CuCl ……..[Ar]3d104s0 ………. Mp 430°C …....r =0.9A

NaCl ………[Ne]3s1…………….mp 801°C ……r = 114 A

HgCl2 ………. 4f14 ……………. Mp 276°C …… r =116A

CaCl2………. 3s23p6 …………… mp 782°C …… r =114A

The stability of a crystal lattice is determined by;

1.The electrostatic attraction forces between the ions. These are proportional to the square of the
distances between the ions.
2.Van der Waals forces of attraction are inversely proportional to the 7th power of the distance
between the ions
3.Interatomic repulsive forces are approximately proportional to the 10th power of the distance
between the ions.

LATTICE ENERGY
A crystal forms if it gives the most farvorable lattice energy.
Lattice energy Is the amount of energy evolved when 1 mole of an ionic compound is formed from
its gaseous ions. Theoretical values can be calculated from;
1
Born-Lande equation: U= -N0Az+z-e2(1- 𝑛)
 4πƹr0
Where;ƹ =permittivity constant 8.854 x 10-12FM-1
A =Madelung constant
N0= Avogadro constant
z+z- are the charges on cation and anion
r0 = the equilibrium interionic distance
e = charge on an electron
n = the Born exponent
since most of the factors are constants
𝑧𝑧
Uα 𝑟
1.The smaller the value r0 the greater the amount of energy involved, the more stable the crystal
lattice.
1
Uα 𝑟
cpd r/A U/kJ/Mole Stability
LiF 2.10 -1004 More
CsI 3.96 -527 Less

However when the ions become too close to touch, their eln clouds repel reducing stability

2.The lattice energy depends on the product of the ionic charges.

Uα z+z-
cpd r/A z+ z- U/kJ/Mole Stability
LiF 2.10 1 -1004 Less
MgO 2.10 2 -3933 more

3.Crystals with a high LE usually melt at high temps and are very hard. High lattice energy is
favoured by small interionic distance and a high charge on the ions. LE can be calculated from the
Born-Harber cycle.

Qa) determine the LE of NaCl(s) from;

ΔHfusion of NaCl = -413 kJ/mole

ΔHsubl of Na = 109 kJ/mole
ΔHbde of Cl2 =496 kJ/mole
ΔHI of Na =119.5 kJ/mole
E A of Cl = -350.5 kJ/mole

Using Hess’s law,

ΔHformation = ΔHfusion of NaCl + ΔHsubl of Na + ΔHbde of Cl2 + ΔHI of Na + E A of Cl + U

b) Construct the Born-Harber cycle for this process

Effects of;
1.hydration of ions on structure
Ionic solids are usually soluble in water because the dipole on water interact with the charges on
the ions. The strength of the interaction increases with decreasing cation size and increasing
charge. Strong coordination may lead to the formation of hydrates e.g [Al(H2O)6]3+.3Cl-

2.Coordination number
𝑟+
The ion’s coordination can be predicted by 𝑟 −

𝑟+ Preferred (CN)
𝑟−
Less 0.732 8 ; Cubic
0.414-0.732 6; octahedral
0.225-0.414 4; tetrahedral

COVALENT BOND
Is a linkage between 2 non-metallic atoms by sharing electrons. In some cases the shared elns are
donated by a single species. In such a case the covalent bond is referred to as coordinate/dative
bond.
A: + B A+ : B -
The formed species are charged.
a). show bonding in NH4+
b).show bonding in CO
c).explin why HCl gas in water is acidic
d).why does ice float on water.

POLAR AND NON-POLAR COVALENT BONDS

Polarity refers to the unequal attraction of elns in elements of a cpd resulting in a molecule with a
negatively charged end and a positively charged one. This is brought about by the electronegativity
difference of the constituent elements. This exerts the unequal attraction of the bond elens creating
net difference in the charge over the molecule. The greater the Δ𝒳 the more ionic the bond
Generally ; non-polar bonds Δ𝒳< 0.4, Polar ones 2> Δ𝒳> 0.4
Ionic Δ𝒳 >2
e.g H-Cl Hᵟ+Clᵟ- Δ𝒳=2.7-2.1 =0.6 hence polar covalent bond
the result is a bond where the electron pair is displaced towards the more electronegative
one acquiring δ+ and δ- which gives the molecule a dipole.
A molecule in which the dipoles cancel each other results into a molecule not being polar.

In the first case the polarities are not equal so they do not fully cancel out but in the second one
they fully cancel making the molecule non-polar
Polarity determines;
a). molecules shapes since the unequal pull of elns affects the spatial orientation of the molecules
b). surface tension
c) solubility, polar molecules interact with water molecules through the hydrogen bonds and
inductive effects.
d) melting and boiling points

VAN DER WAAL’S FORCES

The attraction and repulsion between particles and surfaces are significant in the adsorption of
surfactants at interfaces, adhesion, stability of colloids and micellization of surfactants. Van der
Waals forces involvemomentary attraction between molecules and atoms. They are responsible for
coagulation of colloids and coalescence of drops and bubbles.

In 1973 Van der Waal suggested corrections to the ideal gas equation.
𝑃𝑉
=R where R is a constant
𝑇
PV= RT for n=1
PV=Nrt
𝑛2
For real gases; (P+ 𝑉 2 a)(V-nb)= nRT, this arises from the attraction between molecules for both
polar and non-polar. He proposed presence of;
i) Short range repulsive forces giving rise to the volume constant (b)
ii) Long range attraction forces which lead to constant(a)
The total Van der Waals attraction between the molecules has 3 components
i) Attraction between induced dipoles-London forces
ii) Interaction between 2 permanent dipoles- Keesom orientation forces
iii) Attraction between one permanent dipole and an induced one-Debys induction force
Consequently,
a) Movement of electrons cause rapidly fluctuating dipoles on neutral molecules, Br-Br
b) Induced dipoles, a nonpolar molecule can be induced due to closeness of a polar molecule;
H-H……. OH2.
The synchronized movement of electrons can occur over a large number of molecules enabling a
solid lattice to be held together.
The more elns you have the more distances over which they can more, the bigger the possible
temporary dipoles and therefore the bigger the Van der Waals forces. Long thin molecules can
develop bigger temporary dipole.

FORMATION OF COVALENT BONDS

There are four different but related approaches to explain how atoms combine to form covalent
bond:
1) Lewis dot structure.
2) Valence Shell Electron Pair Repulsion theory (VSEPR).
3) Hybridization of atomic orbital.

In this lesson we will describe the interactions between atoms called chemical bonds. Most of our
discussion will centre on the simplest method of representing chemical bonding, known as the
Lewis theory. We will explore, however, another relatively simple theory, one for prediction
probable shape-Valence – Shell Electron – Pair Repulsion (VSEPR) theory. The subject of
chemical bonding in more depth will be examined in SCH 200-(Atomic Structure and Chemical
Bonding), especially molecular orbital theory.

Lewis Theory
Some fundamental ideas in Lewi’s theory are:
1. Electrons, especially those of the outermost (valence) electronic shell, play a fundamental
role in chemical bonding.
2. In some cases electrons are transferred from one atom to another. Positive and negative
ions are formed and attract each other through electrostatic forces called ionic bonds.
3. In other cases one or more pairs of electrons are shared between atoms; this sharing of
electrons is called a covalent bond.
4. Electrons are transferred, or shared, in such a way that each atom acquires an especially
stable electron configuration. Usually this is a noble gas configuration, one with eight
outer shell electrons, or an octect.

Lewis Symbols and Lewis Structures

A Lewis symbol consists of a chemical symbol to represent the nucleus and core (inner shell)
electrons of an atom, together with dots placed around the symbol to represent the valence (outer
shell) electrons.

Examples.
Lewis structure for: Na electron configuration [Ne]3s1 is
Na
N electron configuration [He]2s22p3 is
N
O electron configuration [He]2s22p4 is
O
Study question
1 Write the Lewis symbols for the following elements: H, He, Li, C, N, O, F, Ne, Cl,
Na, Mg, Al, K and Ca.

A Lewis structure is a combination of Lewis symbols that represent either the transfer or sharing
of electrons in a chemical bond.

 Ionic bonding (transfer of electrons)

+ -
Na + Cl Na Cl

-
Cl
2+
Mg + 2 Cl Mg -
Cl

 Covalent bonding (sharing of electrons

Hydrogen molecule is written showing a pair of dots between hydrogen atoms, incating that the
hydrogen share the pair of electrons in covalent bond

H + H H H

Two hydrogen A hydrogen

atom molecule
The shared pair is usually represented by a line. E.g. H H

Atoms other than hydrogen also form covalent bonds

H + Cl H Cl

Cl + Cl Cl Cl
Exercise
1 Write Lewis structures of the following ionic compounds:
a) BaO; b) MgCl2; c) Aluminium oxide

2 Write Lewis structures of the following covalent compounds:

a) F2; b) H2O; c) NH3 d) CH4 e) O2 f) N2
 Lewis Structures and Resonance
The Lewis structure of ozone O3are:

O O O or O O O
Which of the two Lewis structure for O3 is correct?

In fact, neither is correct by itself. Whenever it is possible to write more than one Lewis structure
for a molecule the actual electronic structure is an average of the various possibilities called a
resonance hybrid.

Ozone does not have:

 One O=O double bond and
 One O-O single bond as individual structure imply, rather ozone has two equivalent O-O
bonds that one can think of as having a bond order of 1.5 midway between pure single
bond and pure double bond. Both have an identical length of 1.28 Å.

The idea of resonance between two or more Lewis structure is indicated by drawing the individual
Lewis structure and using double headed “resonance arrow” to show that both contribute to the
resonance hybrid.

O O O O O O

Study question
Draw the resonance structure of carbonate ion, CO32-.

Molecular Geometry and Bonding Theories

4.2.1 Valence Shell Electron Pair Repulsion Theory (VSEPR)

(Molecular geometry or shape of molecules)
 Lewis structures say nothing about bond angles.
 A structure should be considered which let all the electron pairs of the valence shell of
central atom try to get further away from each other. Repulsion between lone pairs is
greater than those between bonding electrons.

The order of repulsive energy is: Lp-Lp>Lp-Bp>Bp-Bp

O C O Linear

H Cl Linear
 O
H H V-shaped

Cl

B Trigonal planar
Cl Cl

N
H H Triangular pyramidal
H

C H Tetrahedral
H H

Covalent Bonding and Orbital Overlap

The VSEPR model is a simple method which allows us to predict molecular geometry BUT it
does NOT explain why bond exist between atoms.

 How can we explain molecular geometry and basis of bonding at the same time?
o Quantum mechanism and molecular orbitals are used.

Valence Bond Theory (VBT)

 Combine Lewis idea of electron pair bonds with electron orbitals (quantum mechanic).
 Covalent bond occurs when atom shares electrons.
 Concentrate electron density between nuclei.
 The build up of electrons density between two nuclei occurs when a valence atomic
orbital of one atom overlap with one of another.
 The orbital share a region of space i.e. they overlap.
 The overlap of orbital allows two electron of opposite spin to share the common space
between the nuclei forming a covalent bond.

 In the hydrogen m molecule for instance the H-H bond result from overlap of two singly
occupied H 1s orbitals.
 H + H H H

1s 1s H2
molecule

 In the valence bond model, the strength of covalent bond depends on amount of overlap.
The greater the overlap, the stronger the bond. This in turn, means that bond formed by
overlap other than s- orbitals have directionalities to them.

In the fluorine molecule, F2, for instance each atom has electron configuration:

[He]2s22pz22py22px1

Meaning that the fluorine bond results from overlap of two singly occupied two 2p orbitals. The
2p orbitals must point directly to one another for optimum overlap to occur, and the F-F form bond
along the orbitals.

F F
F + F

2p 2p F2
molecule
F F
atom atom

In HCl, the covalent bond involves overlap of 1s orbital (nondirectional) with chlorine 3p orbital
and formed along p-axis.

1s 3p HCl molecule

The key ideas of valence bond theory can be summarized by few statements:
i. Covalent bonds are formed by overlap of atomic orbitals, each of which contains 1
electron of opposite spin.
ii. Each of the bonded atoms maintains its own atomic orbitals, but the electron pair in the
overlapping pair is shared by both atoms.
iii. The greater the amount of orbital overlap the stronger the bond. This leads to a
directional character to the bond when other than s – orbitals are formed.
 Molecular Geometry and Hybrid Orbitals
Hybrid Orbitals
For polyatomic molecules we would like to be able to explain:
The number of bonds formed
Their geometries

sp Hybrid Orbitals

Consider the Lewis structure of gaseous molecules of BeF2:

 The VSEPR model predicts this structure will be linear

 What would valence bond theory predict about the structure?

The fluorine atom electron configuration:

 1s22s22p5

 There is an unpaired electron in a 2p orbital

 This unpaired 2p electron can be paired with an unpaired electron in the Be atom to form
a covalent bond

The Be atom electron configuration:

 1s22s2

 In the ground state, there are no unpaired electrons (the Be atom is incapable of forming a
covalent bond with a fluorine atom
 However, the Be atom could obtain an unpaired electron by promoting an electron from
the 2s orbital to the 2p orbital:
 This would actually result in two unpaired electrons, one in a 2s orbital and another in a 2p
orbital

 The Be atom can now form two covalent bonds with fluorine atoms
 We would not expect these bonds to be identical (one is with a 2s electron orbital, the
other is with a 2p electron orbital)

However, the structure of BeF2 is linear and the bond lengths are identical

 We can combine wavefunctions for the 2s and 2p electrons to produce a "hybrid" orbital
for both electrons
 This hybrid orbital is an "sp" hybrid orbital

 The orbital diagram for this hybridization would be represented as:

Note:

 The Be 2sp orbitals are identical and oriented 180° from one another (i.e. bond lengths
will be identical and the molecule linear)
 The promotion of a Be 2s electron to a 2p orbital to allow sp hybrid orbital formation
requires energy.
o The elongated sp hybrid orbitals have one large lobe which can overlap (bond)
with another atom more effectively
o This produces a stronger bond (higher bond energy) which offsets the energy
required to promote the 2s electron
sp2 and sp3 Hybrid Orbitals

Whenever orbitals are mixed (hybridized):

 The number of hybrid orbitals produced is equal to the sum of the orbitals being
hybridized
 Each hybrid orbital is identical except that they are oriented in different directions

BF3

Boron electron configuration:

 The three sp2 hybrid orbitals have a trigonal planar arrangement to minimize electron
repulsion

NOTE: sp2 refers to a hybrid orbital being constructed from ones orbital and twop orbitals.
Although it looks like an electron configuration notation, the superscript '2' DOES NOT refer to
the number of electrons in an orbital.

 An s orbital can also mix with all 3 p orbitals in the same subshell

CH4
Thus, using valence bond theory, we would describe the bonds in methane as follows: each of
the carbon sp3 hybrid orbitals can overlap with the 1s orbitals of a hydrogen atom to form a bonding
pair of electrons

NOTE: sp3 refers to a hybrid orbital being constructed from ones orbital and threep orbitals.
Although it looks like an electron configuration notation, the superscript '3' DOES NOT refer
to the number of electrons in an orbital.

ANOTHER NOTE: the two steps often observed when constructing hybrid orbitals is to 1)
promote a valence electron from the ground state configuration to a higher energy orbital, and
then 2) hybridize the appropriate valence electron orbitals to achieve the desired valence
electron geometry (i.e. the correct number of hybrid orbitals for the appropriate valence electron
geometry)

H2O

Oxygen
4.5 Hybridization Involving d Orbitals

Atoms in the third period and higher can utilize d orbitals to form hybrid orbitals

PF5

Similarly hybridizing one s, three p and two d orbitals yields six identical hybrid sp3d2 orbitals.
These would be oriented in an octahedral geometry.

 Hybrid orbitals allows us to use valence bond theory to describe covalent bonds (sharing
of electrons in overlapping orbitals of two atoms)
 When we know the molecular geometry, we can use the concept of hybridization to
describe the electronic orbitals used by the central atom in bonding

Steps in predicting the hybrid orbitals used by an atom in bonding:

1. Draw the Lewis structure

2. Determine the electron pair geometry using the VSEPR model

3. Specify the hybrid orbitals needed to accommodate the electron pairs in the geometric
arrangement

NH3

1. Lewis structure

2. VSEPR indicates tetrahedral geometry with one non-bonding pair of electrons (structure
itself will be trigonal pyramidal)

3. Tetrahedral arrangement indicates four equivalent electron orbitals

Valence Electron Pair Number of Orbitals Hybrid Orbitals

Geometry

Linear 2 Sp

Trigonal Planar 3 Sp2

Tetrahedral 4 Sp3

Trigonal Bipyramidal 5 sp3d

 Octahedral 6 sp3d2

4.6 Multiple Bonds and Orbital Overlaps

Two types of bond

Sigma (σ) and pi (π) bonds

The "internuclear axis" is the imaginary axis that passes through the two nuclei in a bond:

The covalent bonds we have been considering so far exhibit bonding orbitals which are
symmetrical about the internuclear axis (either an s orbital - which is symmetric in all directions,
or a p orbital that is pointing along the bond towards the other atom, or a hybrid orbital that is
pointing along the axis towards the other atom)

Bonds in which the electron density is symmetrical about the internuclear axis are termed
"sigma" or "" bonds

In multiple bonds, the bonding orbitals arise from a different type arrangement:

 Multiple bonds involve the overlap between two p orbitals

 These p orbitals are oriented perpendicular to the internuclear (bond) axis

This type of overlap of two p orbitals is called a "pi" or "" bond. Note that this is a single
bond (which is made up of the overlap of two p orbitals)
In  bonds:

 The overlapping regions of the bonding orbitals lie above and below the internuclear axis
(there is no probability of finding the electron in that region)
 The size of the overlap is smaller than a  bond, and thus the bond strength is typically less
than that of a  bond

Generally speaking:

 A single bond is composed of a  bond.

 A double bond is composed of one bond and one bond.
 A triple bond is composed of one bond and two bonds.

C2H4 (ethylene; see structure above)

 The arrangement of bonds suggests that the geometry of the bonds around each carbon is
trigonal planar
 Trigonal planar suggests sp2 hybrid orbitals are being used (these would be  bonds)

What about the electron configuration?

Carbon: 1s2 2s2 2p2

 Thus, we have an extra unpaired electron in a p orbital available for bonding

 This extra p electron orbital is oriented perpendicular to the plane of the three sp2 orbitals
(to minimize repulsion):

 The unpaired electrons in the p orbitals can overlap one another above and below the
internuclear axis to form a covalent bond
  This interaction above and below the internuclear axis represents the single bond
between the two p orbitals

Experimentally:

 we know that the 6 atoms of ethylene lie in the same plane.

 If there was a single  bond between the two carbons, there would be nothing stopping
the atoms from rotating around the C-C bond.
 But, the atoms are held rigid in a planar orientation.
 This orientation allows the overlap of the two p orbitals, with formation of a bond.
 In addition to this rigidity, the C-C bond length is shorter than that expected for a single
bond.
 Thus, extra electrons (from the  bond) must be situated between the two C-C nuclei.

C2H2 (acetylene)

 The linear bond arrangement suggests that the carbon atoms are utilizing sp hybrid
orbitals for bonding

 This leaves two unpaired electrons in p orbitals

 To minimize electron replusion, these p orbitals are at right angles to each other, and to
the internuclear axis:

 These p orbitals can overlap two form two  bonds in addition to the single  bond
(forming a triple bond)
Delocalized Bonding

localized electrons are electrons which are associated completely with the atoms forming the
bond in question

In some molecules, particularly with resonance structures, we cannot associate bonding electrons
with specific atoms

C6H6 (Benzene)

Benzene has two resonance forms

 The six carbon - carbon bonds are of equal length, intermediate between a single bond
and double bond
 The molecule is planar
 The bond angle around each carbon is approximately 120°

The apparent hybridization orbital consistent with the geometry would be sp2 (trigonal planar
arrangement)

 This would leave a single p orbital associated with each carbon (perpendicular to the
plane of the ring)

With six p electrons we could form three discrete  bonds

  However, this would result in three double bonds in the ring, and three single bonds
 This would cause the bond lengths to be different around the ring (which they are not)
 This would also result in one resonance structure being the only possible structure

The best model is one in which the  electrons are "smeared" around the ring, and not localized
to a particular atom

 Because we cannot say that the electrons in the  bonds are localized to a particular atom
they are described as being delocalized among the six carbon atoms

Benzene is typically drawn in two different ways:

 The circle indicates the delocalization of the p bonds

4.7 Resonance Structures and Hybrid Orbitals

Structure of NO3-

The Lewis structure of NO3- ion suggests that three resonance structures describe the molecular
structure

 For any individual Lewis resonance structure the electronic structure for the central N
atom is predicted to be sp2 hybrid orbitals participating in  bonds with each of the O
atoms, and an electron in a p orbital participating in a  bond with one oxygen (forming a
double bond)
  Two of the O atoms are predicted to have sp3 hybrid orbitals, with one orbital participating
in a  bond with the central N atom and the other orbitals filled with non-bonding electron
pairs. The other O atom is predicted to have sp2 hybrid orbitals, with one orbital
participating in a  bond with the central N and two orbitals filled with non-bonding pairs
of electrons. Furthermore, this last O atom is participating in a double bond with the central
N atom and therefore should have an electron in a p orbital to participate in a  bond with
the central N

How will this arrangement look as far as the orbital diagrams?

 There are 24 valence electrons in the expected valence orbitals above

 Summing the valence electrons from the formula gives: (3 x 6) for O, plus 5 for N, plus 1
for ionic charge = 24

What might we expect for the electron configuration if we just started with the N atom?
 We would predict that the N can only make two  bonds, it would have one pair of non-
bonding electrons, and a p electron left over to participate in a  bond with one of the 
bonds
 This is different from what the Lewis structure shows, and from our prediction of hybrid
orbitals from the expected geometry
 If we look at the sp3 O atoms above we see that they actually have 7 electrons (1 more than
expected), while the sp2 O atom has the expected 6. Furthermore, the N atom (in the correct
sp2 configuration) has 4 electrons (1 less than expected)
 The "extra" electron from the ionic charge is correctly accounted for in the summation of
electrons