Chapter 4 Bonding Ionic-Metalli and Geometry

Lesson 4.
Molecules and chemical compounds.

Chemical Bonding I
1. Introduction to Chemical Bonding

2. Ionic Bonding
3. Metallic Bonding.
4. Covalent bonding. Lewis model
5. Molecular geometry.
General Chemistry. USP-CEU

1. Introduction
silver
Constituents of matter are either many
atoms of the same type (elements) or of
Salt
different types (compounds) METALLIC
IONIC
Atoms are held together by chemical bonds
sugar
Properties of matter depend on nature of bonding while nature of
bonding depends on electronic structure of bonded atoms
COVALENT
Their position in the periodic table

1. Introduction
With Electronegativity difference (ΔEN)

we are able to asses the most likely
type of bond that will be formed by
those atoms when they combine to form
a compound

1. Introduction
Metals
Non Metals
• IONIC BONDING : metal - non metal combination

Ionic compounds. Example: NaCl
• COVALENT BONDING: non metal - non metal combination

Molecular compounds Example: Cl2, CO2
• METALLIC BONDING: metal - metal combination

(inter)metallics compounds Example: Li, CuSn, CuZn
2. Ionic Bonding
2.1. Introduction
2.2. Crystalline structure
2.3. Lattice energy, Hess law and Born-Haber cycle
2.4. General properties
2.5. Fajan’s rules: covalent contribution to ionic bonding

2.1. Ionic Bonding. Introduction
The origin of an ionic bond is the electrostatic force of attraction between ions that carry
opposite electrical charges.
Tendency to reach noble gas configuration produce positive ions of metals and negative ions
of non metals
Typical ionic compounds are formed by element of very different electronegativity (∆EN > 1.7):
metals and non metals.
Metals tend to
Non metals
lose electrons
tend to get
extra electrons
Cl + e– → Cl–
Na → Na+ + e–
Oxidizing
Reducing agents
agents
2.1. Ionic Bonding. Introduction
Formation of an ionic compound is
exothermic
(releases energy to the environment)
https://www.youtube.com/watch?v=d2geiGKFveE
Formation of ions and IONIC SOLIDS , ordered ions forming a

rearrangements of ions crystalline structure
Ions are held together in the crystal by electrostatic interactions

2.2. Crystalline structures of ionic compounds
The so called structure is tridimensional arrangement of ions arising from

the balance of attraction (ions of opposite charge) and repulsion forces
ions with the same charge)
For an ionic couple we

Repulsion can also find repulsion forces!
V
Final Potential Energy
Attraction
The potential energy of an ionic couple
as a function of interionic distance d
The number of nearest-neighbour ions of opposite charge

of a central ion is called coordination number (c.n.)
c.n. Cl– = 6
c.n. Na+ = 6
An imaginary polyhedron defined by the central ion

and its nearest neighbours is called coordination
polyhedron
[NaCl6] Octahedron
In spite of the existence of thousands of ionic compounds only few structures are
found which are called structural types. Thus, many compounds crystallize in the
same structural type: they are isostructural compounds.
http://www.3dchem.com/
Structural type Coordination

MX Cesium chloride CsCl 8:8 cube
MX Sodium chloride NaCl 6:6 octahedron

Blende (cubic) ZnS 4:4 Tetrahedron
Wurtzite ZnS 4:4 Tetrahedron
MX2 Fluorite CaF2 8:4 cube/tetrahedr

Rutile TiO2 6:3 octahedron/
trigonal
MX2
Cristobalite SiO2 4:2 Tetrahedron
/lineal
2.3. Lattice Energy, Hess Law and Born-Haber cycle
Lattice energy, U0
The lattice energy of a mole of positive and negative ions corresponds to the
total energy of all electrostatic interactions, and it can be defined as it follows:
The quantity of energy released in the formation of one mole of a

crystalline solid from its separated gaseous ions when going from an
infinite distance to their positions in the crystalline lattice
Na+(g) + Cl–(g) → NaCl(s) + U0
Lattice energy cannot be measured experimentally

But it can be determined by an indirect method or calculated theoretically
Theoretical calculation of U0 : Born – Landé equation
1 N A Z+ Z−e 2  1 
U0 = − A 1 - 
4 πε 0 d0  n
ε0 vacuum permittivity = 8.854∙10–12 C2∙J–1∙m–1
NA Avogadro’s number = 6.022 ∙1023 mol−1
Z+ y Z– cation and anion charges (Z=1,2,…)
e Elementary charge = 1.602∙10–19 C
d0 distance (given in m) between nearest ions with opposite
charge in the crystalline solid d = r + + r –
A Madelung constant
n Born coefficient

1 N A Z+ Z−e2  1 
U0 = − A 1 - 
4 πε 0 d0  n
Madelung constant (A) takes into account Born coefficient (n) is related to
every repulsion and attraction between all the compressibility of atoms and ions and
ions of the crystal. It only depends on the it only depends on external electronic
structural type configuration
Madelung constants
Ion configuration n

Example: Calculation of U0 for NaCl 1 N A Z+ Z−e2  1 

using Born-Landé eq.: U0 = − A 1 - 
4 πε 0 d0  n
ε0 = 8.854∙10–12 C2∙J–1∙m–1 ANaCl = 1.7476
1/(4πε0) = 8.988∙109 C–2∙J∙m dNaCl = 281 pm=2.81∙10–10 m
NA = 6.022∙1023 mol–1 (NaCl ionic couples) e = 1.602∙10–19 C
nNa+ = 7 ; nCl– = 9 ; nNaCl = (7+9)/2 = 8
8.988x109 x 6.022 x 1023 x 1.6022 x 10(–19)x2

U0 = – x 1.7476 x (1- ⅛)
2.81 x 10 –10
U0 = – 754.1 kJ·mol–1
Units of U0:= J·mol–1
“experimental data” (BH): U0(exp.) = – 781. 4 kJ⋅mol-1
How do we obtain experimental U0 ?

Hess law and Born-Haber cycle
Henry Hess
(1840)
Hess Law :
“If a process occurs in stages or steps (even if only hypothetically), the
enthalpy change for the overall (net) process is the sum of the enthalpy
changes for the individual steps.”
Hess law can be considered a particular case of the law

of conservation of energy
Energy is neither created nor destroyed

C (s) (graphite) + ½ O2(g) → CO (g) ∆H°r= ?
C + O2
CO + ½ O2 ? = – 110.77 kJ
1
–2
∆H1 = –393.75 kJ ∆H–2 = + 282.98 kJ
CO2
(1) C(s) + O2(g) → CO2(g) ∆H°1 = – 393,75 kJ/mol
(-2) CO2(g) → CO (g) + ½ O2(g) ∆H°-2= + 282,98 kJ/mol
(1) + (–2) C (s) + ½ O2 (g) + CO2(g) → CO2(g) + CO(g) + ½ O2(g)
C + ½ O2(g) → CO (g) ∆H°r= ∆H°1 + ∆H°-2 = – 110,77 kJ/mol

Let us apply Hess law to formation of an ionic solid: Born-Haber cycle
H2(g) + C(graphite) A previous remark: definition of standard

+ ½ O2(g) enthalpy of formation
0
Entrhalpy of Formation
– The standard enthalpy of formation of a

Formation enthalpy substance is the enthalpy change that occurs
∆H0f = – 108.6 kJ·mol–1 in the formation of 1 mole of the substance in
the standard state from the reference forms
of the elements in their standard states
– The standard formation enthalpy of a pure

element in its most stable form is 0.
HCHO
Negative enthalpies of formation correspond to
thermodynamically stable compounds
Born-Haber cycle for NaCl
∆H0f
Na(s) + ½ Cl2(g) NaCl(s)
∆Hsub ½ ∆Hdis
Na(g) Cl(g) U0
∆H0f (NaCl) = ∆Hsub(Na) + ∆HI (Na) +

∆HI ½ ∆Hdis (Cl2) + ∆HEA (Cl) + U0 (NaCl)
∆HEA
Na+(g) Cl–(g) U0 exp. (NaCl) =
– 781.4 kJ mol–1

2.4. Some properties of ionic compounds
U0 depends mainly on two magnitudes :
Z+ Z – charge LiF 1022 kJ/mol

U0 ∝
d0 MgO 3927 kJ/mol
U0 increases when Z+ and Z– increase
Size of ions High values of U0
LiF 1022 kJ/mol • Relatively high melting (T.m.) y and
boiling point (T.b.): Solids at room
LiCl 845 kJ/mol
temperature
LiBr 795 kJ/mol
• Low thermal expansion coefficient
LiI 737 kJ/mol
• High hardness
U0 decreases if d0 increases
• Low electrical conductivity in the solid
d0 = r + + r – state and very high in liquid (melted) and
in solution.
– Tm and Tb decrease if U0 decreases
T.m. (CaF2)
T.b.
– Thermal expansion coefficient

is usually small and decreases when U0 increases
(NaCl)
– Hardness decreases when U0 decreases
Hardness
(KCl)

thermal expansion coefficient

Example:
– Electrical conductivity: NaCl conductivity
– Low in the solid state because ion under the

elctrical field are fixed in the structure and
cannot migrate NaCl solid
http://www.youtube.com/watch?v=cZBfXTRZGzY
– High in the melt ; the framework is broken

and ions can move
http://www.youtube.com/watch?v=NfNIn4R8tg4
– High in solution ; hydrated ions can move

The ionic model assumes that charge of ions is spherically distributed
BUT in many cases the charge of ions DOES NOT HAVE spherical
distribution: POLARIZATION.
Polarization can be induced by :
An external electrical field The electrical field due to

proximity of another ion
µ = αE
POLARIZABILITY
POLARIZING POWER
Ideal ionic
compound completely separate, spherical ions
electron densities are apart from each other
However, if the positive ion has a high charge density it can distort the
negative ion by attracting the outer shell electrons to give an area of
electron density between the two species ... a bit like a covalent bond
In the limit

The feasibility of having some covalent character can be predicted using Fajan’s Rules.
A compound is more likely to be covalent if the ...
CATION SMALL SIZE it is “highly polarising” and attracts electrons in the anion
HIGH CHARGE
If charge and radius are the same polarizing power is higher for transition metals than for
those with noble gas configuration
ANION LARGE SIZE it is “highly polarisable” and will be easily distorted

HIGH CHARGE
n.b. Just because a substance is less likely to be covalent according to

Fajan’s Rules doesn’t mean it will be ionic; it will remain ionic Kasimir Fajans
(1887-1975)
but with some covalent character (or vice versa).

The positive ion attracts the

outer shell electrons of the
negative ion and distorts the
spherical ionic shape...
There is now some electron
density between the species
SMALL CATION LARGE ANION

HIGH CHARGE DENSITY ELECTRONS FAR FROM NUCLEUS
HIGHLY POLARISING HIGHLY POLARISABLE

A COMPOUND IS MORE LIKELY TO HAVE
SOME COVALENT CHARACTER IF...
• THE CATION IS SMALL AND/OR HAS A HIGH CHARGE - HIGHLY POLARISING
• THE ANION IS LARGE AND/OR HAS A HIGH CHARGE - HIGHLY POLARISABLE
MORE COVALENT
MORE COVALENT
CHARACTER
CHARACTER
The POLARISING POWER is the ability of an ion to modify

the charge distribution of a neighbour ion or atom.
It can be quantified by the ratio:
Ze
r 2
Note that cations exhibit a polarizing power greater than anions.

NaCl FeCl3 TiCl4
Iónic …. … covalent

POLARIZABILITY of an ion measures how easy

is to distort its charge distribution in the presence
of either an electric field or another ion.
Table shows that anions are more

polarisable than cations
Polarization is reciprocal (cation to anion and anion to cation) but it is

enough taking into account the polarization effect of cation on an anion .
Cations polarize anion and the contrary is neglected.

Different effects of the covalent contribution on ionic compounds

1. Differences between U0 (exp) and U0 (th.)
2. Lower coordination number than the expected by consideration of radius ratio rc/ra:
3. Decreasing of structure dimensionality
Tridimensional Layered Chain molecular
NaCl FeCl3 BeCl2 TiCl4
Na+ 6 Fe3+ 6 Be2+ 4 Ti4+ 4

Cl– 6 Cl– 2 Cl– 2 Cl– 1
– Percentage of covalent character in the M–Cl bond +
3. Metallic bonding
All transition elements

are metals
Kr
Border between metals and

Representative groups : non metals, Metalloids :
metals left, non metals semiconductors
right
metal metalloids non metal

4/ OF ELEMENTS ARE METALS
5
Only 24 elements are typical non metals
3. Metallic bonding
3. Characteristics of metallic bonding
1. Non directional bond

2. Electrons are shared by all atoms
3. All shared electrons contribute to the bond
4. Metals exhibit high compacity structures with high coordination number
A.) The Electron Sea Model
It pictures a solid metal as network of positive ions

immersed in a “sea of electrons”.
Electrons in the sea are free (not attached to any
particular ion) and they are mobile

3. Metallic bonding
B.) Band Theory
Band theory.
• Extension of MO theory.
N atoms with 1 AO /atom
give N orbitals that Metal vapor Crystal metal
are closely spaced in energy.
For LiN:
• N/2 are filled.
The valence band.
• N/2 are empty.
The conduction band.
The valence band is the highest band with electrons in it,
and the conduction band is the highest band with no electrons in it.

3. Metallic bonding
Metal: conduction band partially filled with electrons
CB Conduction
band
Valence
VB
Conduction band band
Metal Metal
CB Conduction
band
gap
Valence band
VB Valence
band
Insulator Semiconductor
3. Metallic bonding
Example: band structure of metallic litihium
N atoms of Li forming a crystal

N atoms of Li
e. conf. 1s2 2s1
2p band with 6N states
(empty)
2s band with 2N states,

Half filled
energy
GAP OF ENERGY
1s band with 2N states
(full occupied)
In the GAP there are not states for electrons: there are not orbitals
with those energies

3. Metallic bonding
Strenght of Metallic Bonding
It correlates to heats of vaporization or atomization ∆Hvap
∆H vap
Bond energy ∆Hvap<=> Bond energy

Metal (s) Metal (g)
Energy of metallic bonding depends on:

a) Energy of atomic orbital that overlap to form bands
b) The number of electrons that become delocalized from the metal
c) Charge and radius of the “cation”
Energy O.A. ↑ Number of electrons ↑

ΔHvap ↓ ΔHvap ΔHvap ↑
3. Metallic bonding
Strenght of metallic bonding through the periodic table (energy) and properties
∆Hvap variation in s and p metals:
a) Groups: as a general trend ∆Hvap decreases from top to bottom
190
Li Na K Rb
170
150 ∆H vap 163 108 83 79
∆H vap (kJ mol-1)
130 (kJ·mol-1)
110
90
70
50
Li Na K Rb Cs
Number of electron that become delocalized is constant (one for this case)
From top to bottom EAO increases while r atom increases : thus ∆H vap decreases

3. Metallic bonding
b) Short periods : ∆H vap increases from left to right
Na Mg Al
∆Hvap (kJ · mol-1) 108 149 326
ratom (pm) 190 160 143
e– becoming 1 2 3
delocalized in the band
From left to right in the period the number of electrons that become delocalized
in the band increases
Besides, E AO decreases due to the increasing of effective nuclear charge

3. Metallic bonding
Properties of metals All metals exhibit a common set of physical and chemical properties
Density Mechanical properties related to

Malleability and crystalline structure
Ductility, Hardness
Gray color (metallic) Optical properties related to band
opaque structure ( bonding))
Metallic sheen
Thermal conductivity Thermal properties related to both
Wide range of Tm and Tb crystalline and band structures
Electrical conductivity Electrical properties related to band

structure
Wide variety of Magnetic properties related to band

magnetic properties structure

3. Metallic bonding
Thermal properties
Melting point of the elements
unknown

3. Metallic bonding
Melting and boiling points vary similarly to ∆H vap:

∆H vap ↑ … Tm and Tb ↑
- Alkali metals : low Tm/Tb.

- d-metals: in general high Tm/Tb
- Central elements of d-block: the highest Tm/Tb (refractory metals)
Thermal expansion coefficient: metals with high ∆H vap exhibit low

thermal expansion coeffient
Specific heat: in general it is low in the metals.

They present high heat (thermal) conductivity

3. Metallic bonding
Mechanical properties
a) Density: the high coordination (8 or 12) typical of the metals determines its
high density. It depends on the atomic mass and r met
Density
[g/cm3]
Atomic number
b) Hardness and mechanical resistance (torsion and compression): related to the

strenght of Me-Me bond.
The higher ∆Hvap the harder the metal is.
3. Metallic bonding
Light metals: ρ < 5 g·cm-3
The rest of them … heavy metals

3. Metallic bonding
Two important characteristic of metals are Malleability and Ductility
Metals can be conformed as sheets without being broken:
Gold leafed
Fracture, brittle
Ionic crystals Metallic crystal
Roman coin:
Emperor Augustus
(ehc3. Metallic bonding
o hcp) (ecc
(ehco occc)
hcp)
Hexagonal close packed (hcp) Cubic close packed (ccp)
Structures of metals
In plane coordination is 6
Example: Mg Example: Cu

3. Metallic bonding
Chemical properties: reactivity
It is related to the stability of the different oxidation states
Assesed by thermodynamic criteria
In the solid state ∆Gº = ∆Hº - T∆Sº
Ionic compounds: Born-Haber cycle
mM(s) + n/2 X2(g) MmXn(s)

∆Hv n/2 ∆Hd
mM(g) n X(g) ∆Hv ∆Hi and U0 are the most

U0 important parameters related
m (∆HI)n n (∆HAE)m to metal nature
mMn+(g) + nXm-(g)

3. Metallic bonding
Covalent compounds:
M(s) + n/2 X2(g) MXn(s)

∆Hv n/2 ∆Hd
n ∆Hbonding
M(g) + n X(g)
∆Hvap y ∆Hb are the important
parameters related to metal
nature

3. Metallic bonding
Reactivity in aqueous solution: ∆Gº = ∆Hº - T∆Sº = - n F Eº

M(s) Mn+(aq) + ne-
∆Hv
M(g)
(∆HI)n ∆Hhydration
Mn+(g)
∆Hvap, ∆HI y ∆Hhyd are

parameters related to metal
nature

3. Metallic bonding
Stability of oxidation states
It depends whether the metal is in solution, in a solid or in forming a complex.
In the solid state and complexes unusual oxidation states can be stabilised
Ex: FeSO4*7H2O Fe+2 is stable in the solid. Upon dissolving the salt
Fe+2  Fe+3 (more stable in solution).
Most stable oxidation state in solution :

s elements :
Alkali I: Li+1, Na+1, K+1, Rb+1, Cs+1

Alkaline-earth II: Be+2, Mg+2, Ca+2, Sr+2, Ba+2
Cations are colorless and diamagnetic (noble gas configuration)

3. Metallic bonding
p metals Several oxidation states
In general more stable the lowest
Cations colorless and diamagnetic (configurations nd10 y nd10(n+1)s2)

3. Metallic bonding
d metals Variable oxidation states
1st series
3 4 5 6 7 8 9 10 11 12
Different colors (electronic

transitions) and paramagnetic (with
n unpaired electrons) µ= √n(n+2)

3. Metallic bonding
2nd and 3rd Series de ∆Hi decreases down a group stabilising
transición higher oxidation states
Different colors (electronic

transitions) and paramagnetic (with
n unpaired electrons) µ= √n(n+2)
3. Metallic bonding
Optical and electrical properties
a) Electrical conductivity : metals are good electrical conductors due to the existence of
energetic states (orbitals) above the Fermi level available for electrons. Half-filled bands or
overlapping of bands)
Conductivities (105 Ω–1cm–1) and
resistances (10–6 Ω cm)
b) Optical properties: Opaques and metallic shine Half-filled bands or overlapping of bands
Lewis Theory
Gilbert Newton Lewis
(1875-1946)
“Electrons, specially those of the outermost (valence) electronic shell,

play a fundamental role in chemical bonding (shared or transferred).
“Noble gases are inert because of their stable electronic

configuration: atoms of other elements combine with one another
to acquire similar electron configurations. They tend to have an
outer shell with 8 electrons, octet (valence shell).
Petrucci 10th Ed., Chapter 10

Octet rule
 The elements of the main groups (s and p block) but hydrogen, tend
to complete the octet in the outer shell to reach noble gas configuration.
 Elements of second period (n=2) have got only s and p orbitals and
they can be occupied by 8 electrons as the maximum (no exceptions).
 Elements belonging to higher periods can accept more than 8

electrons due to the presence of d orbitals.
Example: PCl5 exists

NCl5 does not exist
 Transition elements follow a similar rule: the 18-electrons rule

1. Electrons,of the outermost electronic shell, play a fundamental role

in chemical bonding (shared or transferred).
2. Transfer of electrons yields to ionic bonds
• •• 2+ • 2-
BaO Ba • O
• • Ba O
•••
••
•• ••
3. Sharing of electrons yields to covalent bonds.
•• •• •• ••
F + F F F
••
••
••
••
••
•
•• •• •• ••
4. Electrons are either transferred or shared in order to complete the
octet (noble gas configuration)
Lewis symbols
A chemical symbol that represents the
nucleus and either the transfer or the
sharing of electrons in a chemical bond
Electrons of the outermost electronic shell or
valence electrons are represented by dots
around the chemical symbol.
A set of elements of the

periodic table:
Elements belonging to the

same group of the periodic
table

Some examples H2
F2
•• •• ••
CCl4 on the basis of C: [He] 2s2 2p1 2p1 Cl C Cl
••
••
••
••
Cl: [Ne] 3s2 3p2 3p2 3p1 •• ••
C atoms does not fulfil the
octet rule
Two paired electrons not participating in the bond (lone pair) can be
unpaired (excited state) and further reaction with chlorine justified:
•• –
Cl Cl
–
–
••
••
C*: [He] 2s1 2p1 2p1 2p1 •• •• •• – –
–
Cl C Cl Cl – C – Cl
–
Cl: [Ne] 3s2 3p2 3p2 3p1
–
••
•• ••
•• ••
••
•• •• •• – –
–
Cl Cl
–
–
Note the difference between lone pair and bond pair •• –

•• –
P: [Ne] 3s2 3p1 3p1 3p1 Cl Cl
••
••
–
–
PCl3 •• •• •• – –
Cl: [Ne] 3s2 3p2 3p2 3p1
–
Cl P Cl – –
Cl P Cl
••
••
••
••
–
–
•• •• •• – – –
P has got stable 3d orbitals:
Lone pairs can be unpaired if P is excited: new compounds
P*: [Ne] 3s1 3p1 3p1 3p13d1
PCl5
Cl: [Ne] 3s2 3p2 3p2 3p1
•• –
•• Cl •• – Cl –
–
–
••
••
Cl •• Cl Cl Cl
–
–
••
••
•• P •• – P –
Cl Cl Cl Cl
–
–
••
••
–
–
–
••
••
•• •• –
P does not fulfil the octet rule (usual situation in third period elements)
If more than one pair of electrons are shared by two elements multiple bonds are formed
N2 N: [He] 2s2 2p1 2p1 2p1 N ••

•• N
•• N–
–
–N
–
••
••
–
•• •• – –
CO2 C*: [He] 2s1 2p1 2p1 2p1 O C O – –
O– C – O
••
••
••
••
O: [He] 2s2 2p2 2p1 2p1 •• •• – –
H H H H
•• ••
C 2H 4 C*: [He] 2s1 2p1 2p1 2p1
C •• C–
–C
H: 1s1 •• C
•• •• H H
H H

The term Bond order (b.o.) describes whether a covalent bond is single
(b.o =1) double (b.o=2) or triple (b.o.=3) and it is related to the number of
bond pairs between two atoms.
– – O
– –
O– C – O b.o. C–O = 2 b.o.O–H = 1
– – H H
N–– b.o.N–N = 3
–N
–

Writing Lewis Structures
• All the valence e- of atoms must appear.
• Usually, the e- are paired.
• Usually, each atom requires an octet.
– H only requires 2 e-.
• Multiple bonds may be needed.
– Readily formed by C, N, O, S, and P.
Skeletal Structure
• Identify central and terminal atoms.
H H • Hydrogen atoms are always terminal atoms.

• Central atoms are generally those with the lowest electronegativity.
H C C O H
• Carbon atoms are always central atoms.
H H • Generally structures are compact and symmetrical.
Strategy for Writing Lewis

Structures

Example 1 :SO2
1) Skeletal structure O–S–O
2) Number of valence electrons

S: [Ne] 3s2 3p4 → 6 e– 1S: 6 e–
O: [He] 2s2 2p4 → 6 e– 2O: 12 e–
18 valence e–
3) Number of covalent bonds
Every atom tends to complete the octet:
e– needed for the octets= 2e– x no of H atoms + 8e– x rest of atoms

SO2: 2e– x 0 + 8e– x 3 = 24 e– for octets
Number of bond electrons = no. octets e–– no. valence electrons

SO2: 24 e– – 18 e– = 6 bond e–
Bond numbers = ½ bond e– (each bond is formed by a couple of

paired electrons)
6e – –
SO2: –
2e / bond = 3 bonds O –S–O
4) Non shared electrons
No. of non shared electrons = no. of valence e– – no. of bond e–

SO2: 18 e– – 6 e– = 12 e– non shared (6 pairs)
– – –
O––S–O –
– –
Example 2: ClO3– (chlorate ion)
O – Cl – O
1) Skeletal structure
–
O
2) Number of valence electrons 1 x 7 e– + 3 x 6 e– + 1 e– = 26 e–
3) Number of covalent bonds

e– needed for the octets = 2 e– x 0 + 8 e– x 4 = 32 e–
Number of bond electrons = 32 e– – 26 e– = 6 e– (shared)
6e – = 3 bonds
Bond numbers = 2e – / bonds
(–) – (2+)
– – (–)
4) Non shared electrons O – Cl – O
–
– –
–
O
–
–
26 e– – 6 e– = 20 e– (10 pairs) – (–)
Example 3: NO+ ( nitrosonium ion)
1) Skeletal structure N –O
2) Number of valence electrons 1 x 5 e– + 1 x 6 e– - 1 e– = 10 e–

3 ) Number of covalent bonds
e– needed for the octets = 2 e– x 0 + 8 e– x 2 = 16 e–
Number of bond electrons = 16 e– – 10 e– = 6 e– (shared)

6e – = 3 bonds
Bond numbers = 2e – / bond N––
–O
4) Non shared electrons
10 e– – 6 e– = 4 e– (2 pairs) N–
–
–O
–
–
Formal Charge
The formal charge on an atom in a Lewis structure is the number of valence e- in
the free atom minus the number of e- assigned to that atom in the Lewis structure.
1
FC = nvalence e- - nlone pair e- - nbond pair e-
2
FC are very useful to propose the more likely Lewis structure for a molecule
(a) Where formal charges are required, FC should be as small as possible.

High FC (+2, +3, –2, –3, etc...) are not likely to be stable
(b) Negative FC usually on most electronegative elements.

(c) Neutral molecules: Sum of FC must equal zero and must equal the
magnitude of the charge for a polyatomic ion. FC of same sign on
adjacent atoms is unlikely.
Cations Mn+: Σqform = + n
Anions Xm–: Σqform = – m
Neutral molecules: Σqform = 0

Σqform = 0 + 1 –1 = 0
Examples: 6 – 2 – 6/2 = +1
Neutral molecule
SO2 6 – 4 – 4/2 = 0 6 – 6 – 2/2 = –1

– – –
O –– S – O
–
– (+) – (–)
7 – 2 – 6/2 = +2 Σqform = +2 –1 –1 –1 = –1
ClO3–
(–) – (+2) Anion
– – (–)
O – Cl – O 6 – 6 – 2/2 = –1
–
– –
–
O
–(–) 6 – 6 – 2/2 = –1
–
–
6 – 6 – 2/2 = –1
Σqform = 0 + 1 = +1
(+) Cation
NO+ –
N –– O
–
–
5 – 2 – 6/2 = 0 6 – 2 – 6/2 = +1
Multiple covalent bond to reduce FC
In some cases FC can be decreased in adjacent atoms if multiple bond are

formed; The atom with the negative FC contributes with the two electrons
(+) (–) – – –
O– –O
–S–
– – – – –
O––S–O
–
– –
¿Octet?
(–) (+2) (–)
– – – – – –
O – Cl – O O–– Cl ––O
–
–
– – – –
–
–
O O
–
–
–
–
– –
(–) (–)
Note : A covalent bond in which a single atom contributes with two electron is called a coordinate covalent bond
Resonance
In some cases is possible to find several equivalent Lewis structure and it is not
posssible to chose the more likely structure even by using bond distances .
Example 1: Ozone, O3 Possible structures ?
(+) (–) (–) (+)

– – – – – –
O––O–O O–O– –O
–
–
– – – –
O–O distances in O3 are exactly the same
…neither of them represent the structure but both of

them contribute to the correct structure…….. 117°
the situation is called
Resonance
Resonance structures O3
(+) (–) (–) (+) (–½) (+) (–½)
– – – – – – – – –
O––O–O O–O– –O O–O–O
–
– –
–
– – – –
Resonance hybrid
The arrow does not mean that the molecule has one of the structure
part of the time and the other the rest of the time.
It has the same structure all the time
Resonance or mesomerism is well known in organic compounds
Example: benzene

Example 2: carbonate ion, CO32- (all C–O distances are the same )
Valence e- = 1 x 4 e– + 3 x 6 e– + 2 e– = 24 e–
Octets e- = 4 x 8 e– = 32 e–
Bond e- = 32 e– – 24 e– = 8 e– ⇒ 4 bonds
Unpaired e- = 24 e– - 8 e– = 16 e– ⇒ 8 pairs
Resonance structures of carbonate
– – – – – – – –
–
O– C O – –
O C –O – –
O C O – –
O C O –
–
–
– – – – – – – –
– –
–
– –
– –
(–) (–) (–) (–) (–⅔) (–⅔)
O O O O
–
–
–
–
–
– –
(–) (–) (–⅔)
Bond order C–O: 4/3

(in between single and double )
Exceptions to the octet rule
At times we must depart from the octet rule. There are three types of exception to the octet rule
1. Incomplete Octets
The number of electrons around the central atom is smaller that 8 . It happens for Be, B y Al
Examples: BeH2 Be: 1s2 2s2 2 bonds H – Be – H

– –
BF3 B: 1s2 2s2 2p1 3 bonds F – B –F
–
– –
–
F
–
–
–
It explains the tendency of B to form a coordinate (or dative) covalent bond
– –
H F H F
–
–
–
–
– (+) (–)–
–
–
–
H –N + B– F H –N – B– F
–
–
– –
–
––
––
H F H F
–
–
– –
2. Odd-Electron Species
If the number of valence electrons in a Lewis structure is odd ,

there must be an unpaired electron somewhere in the structure
Examples:
NO (nitrogen monoxide) has 11 valence e– :
•– –
1x5 e– +1x6 e– = 11 e– N–O
–
–
NO2 (nitrogen dioxide) has 17 valence e– :

(+) (–)
– • –
1 x 5 e– + 2 x 6 e– = 17 e– O––N–O
–
– –

3. Expanded Valence Shells
Example : SF6
Lewis structure:
Valence e– = 1 x 6 e– + 6 x 7 e– = 48 e–
Octet e– = 7 x 8 e– = 56 e–
Bond e– = 56 e– – 48 e– = 8 e– ⇒ 4 bonds
Unpaired e– = 48 e– - 8 e– = 40 e– ⇒ 20 pairs
– 2+
F – –
–
–
F
??
–
–
– – – –
SF6 –
F S F –
–
–
– – – –
––
F F
–
–
–
– –

 Some Lewis structures break the octet rule by having 10 or even 12 valence
e- around the central atom creating what it is called expanded valence shell.
••
F –
••
••
F F – Cl –
–
–
Cl Cl
–
–
–
S – P –
F F Cl Cl
–
–
–
–
–
F –
••
••
••
SF6 PCl5
 Expanded valence shells typically involve non metal atoms of the third period
and beyond (they have d orbitals!) that are bonded to highly electronegative atoms

Thus: elements of third period and
beyond can break or not the octet rule
–
– Cl –
–
–
Cl Cl – – –
–
–
PCl5
–
– P – SCl2 Cl – S – Cl
–
– – –
Cl Cl
–
–
–
–
–
–
(+) (–)
– – – – –– –
SO2 O––S–O O––S–O
– –– – –
FC in this case are zero
for the expanded octet

Achievements and limitations of Lewis Theory
Achievements
1. Very straight forward and intuitive that used in the light of (Valence –Shell Electron-
Pair Repulsion) VSEPR Theory allows for the explanation and prediction of the
geometry of many important and common molecules
2. A generalisation of acid and base concepts could be made
– Bases are molecules with one or more lone pairs
– Acids are molecules with any central atom with incomplete octet
– –
H H + H F H F
–
–
–
–
– (+) (–)–
–
–
–
H –N + H+ H –N –H H –N + B– F H –N – B– F
–
– –
–
––
––
–
H H H F H F
–
– –
base acid base acid
Limitations
1. The theory can be applied succesfully only to the first 20 elements
Even in some cases (i.e.: NO, NO2) odd-electron species number do no

fullfill the octect rule
For heavier atoms the exceptions to the Octect Rule is very common (expanded
valence shells)
2. Oversimplification of reality:
Electron are not fixed or in between two atoms. They follow
very complex movement patterns
3. The theory fails to explain extremely important cases, even though ones take into account
resonance:
a) C2 should have a quadruple bond but it has not.
b) The bonds in N2 y O2 are very strong, however in O2+ is stronger than in O2

whereas in N2+ is weaker than in N2
¿Why?
c) How can the molecule H2+ exists ? There are not two electrons to be shared.
A bonding is impossible!!
(there is only one electron)

5. Molecular Geometry
Valence –Shell Electron-Pair Repulsion) VSEPR Theory
We will focus on pairs of electrons in the valence electron shell of a central atom in
a structure to predict molecular geometry and molecular polarity
What do we mean by molecular geometry ?
Tridimensional distribution of nuclei in a

molecule
Most of physical, chemical and

biochemical properties depend
on the molecular geometry

5. Molecular
Characteristic Geometry
parameters to define the molecular geometry are:
Bond distances and bond

angles
H2O
Bond distance: distance between nuclei
Bond angle: angle between the adjacent lines representing
bonds
Molecules with the same stoichiometry may exhibit different molecular geometries
Linear Bent Trigonal Trigonal T-shaped

planar pyramidal

Proposed by Gillespie & Nyholm
VSEPR is based on the repulsion of electron pairs to predict molecular geometry
Molecules are characterised by:

1. A central atom
2. Ligands (bonded to the central atom)
3. A coordination number
(nearest neighbours bonded to the central atom)
Thus, the basic principle in the formation of a molecular geometry is that it

provides:
– The longest distance between non bonded atoms
– The shortest distance between bonded atoms

Ideal arrangements for different coordination numbers
linear trigonal tetrahedral trigonal octahedral pentagonal square

planar bipyramidal bipyramidal antiprismatic
1. Electron pairs repeal each other, whether they are in chemical bonds
(bond pairs) or unshared (lone pairs)
2. Electron pairs assume orientations around an atom to minimize

repulsion. Each orientation is occupied or correspond to one electron-
group

Additional considerations:
1. A group of electrons can be a pair (either lone or bond pair) but also a double or
triple bond. Thus, double and triple bond are considered as single (occupies one
orientation) for geometry purposes
2. Each central atom can be analysed separately.
3. In case of resonance the VSEPR theory can be applied to each (or any)
resonance form
4. The geometry of electron groups and the geometry of the molecule can be
different

Geometry of electron groups and molecular geometry
Note that in the three cases the geometry of electron groups is TETRAHEDRAL:
Notation
VSEPR
Molecular
geometry : Tetrahedral Trigonal Pyramidal Bent
Number of Geometry angles
electron groups
Linear Geometry of electron groups
2
Trigonal
planar
3
Tetrahedral
4
Trigonal
5 bipyramidal
VSEPR
6
Octahedral

5. Molecular Geometry ABn (n=2..6)
The central atom A has not lone pairs

Number of Geometry of Bond pairs Molecular Example
electron groups electron groups geometry
2 2 AB2 CO2
Linear
Linear
3 3 AB3
BF3
Trigonal planar
Trigonal planar
4 4 AB4
CH4
Tetrahedral
Tetrahedral
5 5 AB5
PCl5
Trigonal bipyramidal Trigonal bipyramidal
6 6 AB6 SF6
Octahedral Octahedral
The central atom A has one or more lone pairs
Bond-pair electrons are attracted by two nuclei,

thus they are less expanded and repulsion to BP
other electron groups is smaller.
Nuclei
Lone-pair electrons are attracted by only one

nucleus, thus they spread out more than do bond LP
–pair electrons. As a result the repulsion of lone
pair to other electron groups is larger
Nucleus

The possible repulsive forces are:
1) Bond Pair – Bond Pair (BP – BP)

2) Lone-Pair– Lone-Pair (LP – LP)
3) Bond Pair-Lone Pair (BP – LP)
BP
And the order of repulsive forces: Nuclei

LP – LP > BP– LP > BP– BP
LP
Nucleus
4 BP 3 BP 2 BP
1 LP 2 LP
The central atom A has one or more lone pairs: ABn–mEm
Number of Geometry of Lone Molecular Example
Bond pairs geometry
electron groups electron groups pairs E
3 2 1 O3
AB2E1
Bent
Trigonal planar
3 1 NH3
AB3E1
4
Trigonal
pyramidal
Tetrahedral
2 AB2E2 2 H2O
Bent
5. Molecular Geometry ABn–mEm
Number of Geometry of Bond pairs Lone Molecular
Example
electron groups electron groups pairs E geometry
4 AB4E1 1
SF4
5
Seesaw
Trigonal bipyramidal
3 AB3E2 2 ClF3
T-shaped
2 AB2E3 3
XeF2
Linear
6 5 AB5E1 1 IF5
Square pyramidal
Octahedral
XeF4
4 AB4E2 2
Square planar
Example 1: NH3 Lewis structure

–
H –N – H
Lone pair and bond pair are considered as electron groups:
–
H
4 electron groups to be distributed in the space around N
atom
3 bond pairs + 1 Lone pair: AB3E1

Geometry of electron Molecular
groups geometry
Repulsion LP – BP > Repulsion BP-BP
Tetrahedral Trigonal
pyramidal
∠(HNH)exp. ≈ 107° (109.5° ideal)

Example 2: SO2
Double bonds (4 e - ) are considered as 1 electron group Lewis structure
– – –
–
O–S–O
–
Besides, there are 1 more bond pairs considered as 1 – –
electron group and 1 lone pair
TOTAL: 3 electron groups to distribute around S atom
2 BP + 1 LP : AB2E1
Geometry of electron Molecular

groups geometry Bent
Repulsion LP – BP > Repulsion BP – BP
Trigonal planar Bent
∠(OSO)exp ≈ 119.5º (120° ideal)

Example 3: Acetic acid: CH3COOH (C2H4O2)
Local geometry of complex molecules can be assesed

by application of VSEPR Theory to each central atom
Lewis structure
AB4 AB3 AB2E2
Number of electron 4 3 4
groups
Geometry of electron Tetrahedral trigonal Tetrahedral
groups planar
Expected angles 109.5° 120° 109.5°

Geometry and Molecular Dipole Moments

An electric dipole or dipole moment (μD) arises in molecules where the different charge distribution
of negative (electron) and positive charge (nuclei) is present producing a separation of charges.
Q+ Q– 1 Debye = 3.355·10–30 C⋅m

d – With field +
µ=Q·d
The existence of a molecular dipole depends on:

δ+ δ–
1. Bond dipoles (polar bonds)
2. Molecular Geometry (symmetry)

Orientation of polar molecules
3. Lone pairs in an electric field
(existence and distribution)

1. Bond dipoles
Bond dipoles are key factors for molecular dipole
a) Homonuclear molecules
F F
They are nonpolar: µ = 0
b) Heteronuclear molecules Non polar covalent bond
Due to electronegativity differences bond pairs are not symmetrically distributed

between the nuclei: POLAR BONDS
δ+ δ–
Nucleus
H–F
Gravity center positive charge H F
Gravity center negative charge
H–F
polar covalent bond
The higher the electronegativity difference ∆χ, the more polar is the bond
Polarity and dipole moment
Caution: Polarity and Dipole Moment are not synonymous

Dipole moment is the product of Q and d . Thus molecules with low polarity (with small partial charges)
may exhibit high dipole moment if charge are very far from each other (long interatomic distances)
Example: Nitro- and chlorobencene are non miscibles in water (hydrophobic

and low polarity) but dipole moments are very high .
Compound Dipole moment (D)

Water 1,85
Chlorobencene 2,05
Nitrobencene 4,22

2. Symmetry
The electric dipole moment of a molecule is the sum of all bond dipoles:
bond dipoles For some molecular geometries this SUM es
ZERO though bonds are polarized : linear,
tetrahedral, octahedral, trigonal bipyramidal,
planar simetrical (triangular, square, etc..)
Molecular dipole moment= 0
NON POLAR
bond dipoles
polar
Molecular dipole
moment
POLAR
(µ H2O = 1.84 D)
Non polar Non polar
Non polar

3. Lone pairs
Regions occupied by lone pair can be considered as the negative area with respect to the nucleus to
which they belong; thus lone pair can either reinforce or weaken the molecular dipole moment.
δ– µD Lone pair δ– µD Lone pair
δ– δ+ δ+ δ+
µD total
δ+ δ+ δ– δ–
H N H F N F
µD total
H F NF3
δ+ NH3 δ–
µD bonds µD bonds
µ = 1.46 D µ = 0.24 D

Limitation of VSEPR theory
Deviation from ideal structures are usually observed:
1. Lone pairs (non bonding) of central atom are considered as an electron group as bond
pair are also considered. However, lone pair need more space , are more expanded
Examples:
CH4 NH3 OH2
∠HAH 109.5° 107.3° 104.5°
2. Same as 1) for double bonds… they 3.) …and triple bonds even more
need more space than single bonds than double bonds
Sulphuryl chloride
Examples:
∠FSF = 98° ∠FPF = 102°

thiazyl trifluoride Phosphoryl trifluoride
4. More electronegative ligands produce smaller bonding angle
Example: OH2 104.5°

OF2 103.2°
5. More electronegative central atoms produce larger repulsion between ligands

(larger bonding angle)
Example: NH3 106.7°

PH3 93.3°
6. Lone pair of d electrons of transition metals do not have any influence on

geometry
→ very important when analyzing coordination compounds

Chapter 4 Bonding Ionic-Metalli and Geometry

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Chapter 4 Bonding Ionic-Metalli and Geometry

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Lesson 4.

Molecules and chemical compounds.

1. Introduction to Chemical Bonding

General Chemistry. USP-CEU

Their position in the periodic table

With Electronegativity difference (ΔEN)

General Chemistry. USP-CEU

• IONIC BONDING : metal - non metal combination

• COVALENT BONDING: non metal - non metal combination

• METALLIC BONDING: metal - metal combination

2.2. Crystalline structure

2.3. Lattice energy, Hess law and Born-Haber cycle

2.4. General properties

2.5. Fajan’s rules: covalent contribution to ionic bonding

General Chemistry. USP-CEU

Formation of ions and IONIC SOLIDS , ordered ions forming a

Ions are held together in the crystal by electrostatic interactions

The so called structure is tridimensional arrangement of ions arising from

For an ionic couple we

The number of nearest-neighbour ions of opposite charge

An imaginary polyhedron defined by the central ion

Structural type Coordination

MX Sodium chloride NaCl 6:6 octahedron

MX2 Fluorite CaF2 8:4 cube/tetrahedr

The quantity of energy released in the formation of one mole of a

Na+(g) + Cl–(g) → NaCl(s) + U0

Lattice energy cannot be measured experimentally

Theoretical calculation of U0 : Born – Landé equation

General Chemistry. USP-CEU

General Chemistry. USP-CEU

Example: Calculation of U0 for NaCl 1 N A Z+ Z−e2  1 

8.988x109 x 6.022 x 1023 x 1.6022 x 10(–19)x2

How do we obtain experimental U0 ?

Hess law can be considered a particular case of the law

General Chemistry. USP-CEU

C (s) (graphite) + ½ O2(g) → CO (g) ∆H°r= ?

(1) + (–2) C (s) + ½ O2 (g) + CO2(g) → CO2(g) + CO(g) + ½ O2(g)

C + ½ O2(g) → CO (g) ∆H°r= ∆H°1 + ∆H°-2 = – 110,77 kJ/mol

Let us apply Hess law to formation of an ionic solid: Born-Haber cycle

H2(g) + C(graphite) A previous remark: definition of standard

– The standard enthalpy of formation of a

– The standard formation enthalpy of a pure

∆H0f (NaCl) = ∆Hsub(Na) + ∆HI (Na) +

General Chemistry. USP-CEU

Z+ Z – charge LiF 1022 kJ/mol

– Tm and Tb decrease if U0 decreases

– Thermal expansion coefficient

– Hardness decreases when U0 decreases

General Chemistry. USP-CEU

thermal expansion coefficient

General Chemistry. USP-CEU

– Low in the solid state because ion under the

– High in the melt ; the framework is broken

– High in solution ; hydrated ions can move

General Chemistry. USP-CEU

The ionic model assumes that charge of ions is spherically distributed

An external electrical field The electrical field due to

General Chemistry. USP-CEU

A compound is more likely to be covalent if the ...

ANION LARGE SIZE it is “highly polarisable” and will be easily distorted

n.b. Just because a substance is less likely to be covalent according to

General Chemistry. USP-CEU