1

AOM-2
Architecture of Matters -2

MAXIME FLORENT
[email protected]
AOM-2 2

• Two Teachers for the Lectures (10 sessions)

• Maxime Florent (4 sessions)
• Veronique Bulach (6 sessions online)
• 2 Examination (coefficient 2)
• 1 mid-term exam (0,75)
• 1 final exam (1,25)

• Moodle L1S2 Architecture of Matter 2

(https://moodle.unistra.fr/course/view.php?id=874)
• Lectures, Exercises, Previous Exam
Program 3

• Lewis’s Model (Maxime)

• Geometry of Covalent Molecule (Maxime)
• Molecular Orbital (Maxime)
• Hybridization (Veronique Bulach)
• Molecular Representation (Veronique Bulach)
• Reactivity of molecules (Veronique Bulach)
Lewis’s Model 4
Symbolism
Lewis’s Model 5
Symbolism

1 bond

4 bonds

3 bonds

2 or 1 bonds

1 bond
Lewis’s Model 6
Covalence and Coordinance

1s22s22p5 1s22s22p5

1s1 1s22s22p3
Lewis’s Model 7
Covalence and Coordinance
Coordination Bond: Donation of a pair (donor atom) to an acceptor atom

1s0 1s22s22p5

1s22s22p1 1s22s22p3
Lewis’s Model 8
Ionic Bond
Because of a too high difference in electronegativity, there are not a real bond between these two atoms.
Ionic bond = Electrostatic interaction
Lewis’s Model 9
Octet’s Rule
An atom is surrounded by a maximum of 4 lone pairs (writing convention: line (-) or double dot (:),
binding or not binding
A bonding lone pair by definition is shared between 2 partners,
A non-binding lone pair can be carried by only 1 atom,

Free lone pairs

Free lone pairs

Binding lone pairs Binding lone pairs

Lewis’s Model 10
Octet’s Rule

Binding pair = 2 binding electrons involved in a bond

Free lone pair = 2 non-binding electrons

1s1 1s22s22p3
ev = 1 ev = 5 eb = 6, enb = 2

Total : 5 + 3 = 8 e- Total : 6 + 2 = 8 e-
 Charge = VE – (B/2 + NB)
Lewis’s Model VE = number of Valence electrons
11
Formal Charge B = number of Binding electrons
NB = number of Non-Binding electrons

On C : 4 Binding pairs
0 Lone Pair
C : VE = 4

Formal Charge on C = 4 - 8/2 - 0 = 0

3 Binding pairs On O : 1 Binding pair
1 Lone Pair 3 Lone Pairs
N : VE = 5 O : VE = 6
Formal Charge = 5 - 6/2 -2 = 0 Formal Charge on O = 6 - 2/2 - 6 = -1

On O : 2 Binding pairs
2 Lone Pairs
4 Binding pairs
O : VE = 6
0 Lone Pair
N : VE = 5
Formal Charge on O = 6 - 4/2 - 4 = 0
Formal Charge = 5 - 8/2 - 0 = +1
 Lewis’s Model 12
Multiple Bonds
A double bond = 2 single bonds = 2 Binding pairs = 4 Electrons
A triple bond = 3 single bonds = 3 Binding pairs = 6 Electrons
CO
O : VE = 6 N2
C : VE = 4 C2H4 NO2 N : VE = 5
Total number of e- = 6 + 4 = 10 C : VE = 4 N : VE = 5
Formal Charge C = 4 – 5 = -1 H : VE = 1 O : VE = 6 Total number of e- = 10
-
Formal Charge O = 6 – 5 = +1 Total number of e- = 8 + 4 = 8 Total number of e = 5 + 12 =17 Formal Charge N = 5 – 5 = 0
Formal Charge C = 4 – 4 = 0 Formal Charge N = 5 – 4 = +1
Formal Charge H = 1 – 1 = 0 Formal Charge O1 = 6 – 6 = 0
Formal Charge O2 = 6 – 7 = -1
 Lewis’s Model 13
Hypervalent compounds
Some compound doesn’t respect the Octet’s rule.
Because one of its atom is from the 3rd or lower level on the periodic table
(possess empty D orbitals)
PCl5
P : VE = 5 SF6
Cl : VE = 7 PBr3 SOCl2 S : VE = 6
Total number of e- = 5 + 35 = 40 P : VE = 5 S : VE = 6 F : VE = 7
Formal Charge Cl = 7 – 7 = 0 Br : VE = 7 O : VE = 6 Total number of e- = 6 + 42 = 48
Total number of e- = 5 + 21 = 26 Cl : VE = 7
Formal Charge P = 5 – 5 = 0 Formal Charge S = 6 - 6 = 0
Total number = 6 + 6 + 14 = 26
Formal Charge P = 5 – 5 = 0 Formal Charge F = 7 – 7 = 0
Formal Charge S = 6 – 6 = 0
Formal Charge Br = 7 – 7 = 0
Formal Charge O = 6 – 6 = 0
Formal Charge Cl = 7 – 7 = -1
Lewis’s Model 14
Single electron = Radicals

NO2 NO2+
N : VE = 5 N : VE = 5
O : VE = 6 O : VE = 6
Total number of e- = 5 + 12 =17 Total number of e- = 5 + 12 - 1 = 16
Formal Charge N = 5 – 4 = +1 Formal Charge N = 5 – 4 = +1
Formal Charge O1 = 6 – 6 = 0 Formal Charge O1 = 6 – 6 = 0
Formal Charge O2 = 6 – 7 = -1 Formal Charge O2 = 6 – 6 = 0

The radical compounds are really reactive and most of the time gain or loss one electron
Lewis’s Model 15
Mesomeric effect and resonance

SO2
S : VE = 6
O : VE = 6
Total number of e- = 6 + 12 = 18

Formal Charge S = 6 – 5 = +1 Formal Charge S = 6 – 6 = 0 Formal Charge S = 6 – 5 = +1

Formal Charge O1 = 6 – 6 = 0 Formal Charge O1 = 6 – 6 = 0 Formal Charge O1 = 6 – 6 = 0
Formal Charge O2 = 6 – 7 = -1 Formal Charge O2 = 6 – 6 = 0 Formal Charge O2 = 6 – 7 = -1
Lewis’s Model 16
Mesomeric effect and resonance
CO32-
C : VE = 4
O : VE = 6
Total number of e- = 4 + 18 + 2 = 24

Formal Charge C = 4 – 4 = 0
Formal Charge O1 = 6 – 6 = 0
Formal Charge O2 = 6 – 7 = -1
 Lewis’s Model 17
Mesomeric effect and resonance
Mesomerism refers to the ability of a molecule or ion to form multiple stable forms (called resonance
forms) that differ in the distribution of electrons, but have the same overall charge and number of
atoms.
Degree of unsaturation:

C6H6 C : VE = 4 2𝐶 + 2 + 𝑁 − 𝑋 − 𝐻
H : VE = 1 𝐷𝑜𝑈 =
2
Total number of e- = 24 + 6 = 30

To have a conjugated system is

mandatory to have resonance
forms
 Lewis’s Model 18
Mesomeric effect and resonance
Mesomerism refers to the ability of a molecule or ion to form multiple stable forms (called resonance
forms) that differ in the distribution of electrons, but have the same overall charge and number of
atoms.
hexa-1,3,5-triene
C6H8 C : VE = 4
H : VE = 1
Total number of e- = 24 + 8 = 32

2𝐶 + 2 + 𝑁 − 𝑋 − 𝐻
𝐷𝑜𝑈 = =3
2
Lewis’s Model 19
Mesomeric effect and resonance
 Lewis’s Model 20
Summary
A Lewis Structure is a very simplified representation of the valence shell electrons in a molecule. It is
used to show how the electrons are arranged around individual atoms in a molecule. Electrons are shown as
"dots" or for bonding electrons as a line between the two atoms.
The goal is to obtain the "best" electron configuration, i.e. the octet rule and formal charges need to be
satisfied.

1. Counting the total number of valence electrons

2. Deduct the total number of lone pairs (bonding and non-bonding) to
be placed in the structure using the octet’s rule, when possible
3. Assign the formal charges for each atom
4. Avoid too many charges and respect the electronegativity
Program 21

• Lewis’s Model (Maxime)

• Geometry of Covalent Molecule (Maxime)
• Molecular Orbital (Maxime)
• Hybridization (Veronique Bulach)
• Molecular Representation (Veronique Bulach)
• Reactivity of molecules (Veronique Bulach)
From Lewis to 3D Structure 22

H2O CO32- CH4 SOCl2

Lewis Structure

3D Representation
Geometry of covalent molecules VSEPR 23
Definition
Valence-Shell Electron-Pair Repulsion model

VSEPR model extends Lewis theory to account for molecular shapes

• Rule 1 : Regions of high electron concentation repel one another, so they move as far as possible,
maintaining central atom distance
• Rule 2 : No distinction between single and multiple bonds
• Rule 3 : Only the position of atoms are considered when identify the shape of a molecule
• Rule 4 : Order of repulsion strengths : lone pair-lone pair > lone pair-atom > atom-atom
Valence-Shell Electron-Pair Repulsion 24
model AX
A = Central Atom
z X = Bond

LINEAR TRIANGULAR PLANAR TETRAHEDAL

HCN, CO2 AlCl3, CO32- CH4

TRIANGULAR BIPYRAMIDAL OCTAHEDRAL

PCl5 SF6
Valence-Shell Electron-Pair Repulsion 25
model AX E
A = Central Atom
z Y X = Bond
E = Lone pair

AX3 AX2E1
TRIANGULAR PLANAR BENT

AlCl3, CO32- SO2, SnCl2

Valence-Shell Electron-Pair Repulsion 26
model AX E
A = Central Atom
z Y X = Bond
E = Lone pair

AX4 AX3E1 AX2E2

TETRAHEDAL TRIANGULAR PYRAMIDAL BENT

CH4 NH3, PCl3 H2O, H2S

Valence-Shell Electron-Pair Repulsion 27
model AX E
A = Central Atom
z Y X = Bond
E = Lone pair

AX5 AX4E1 AX3E2

TRIANGULAR BIPYRAMIDAL BUTTERFLY T-SHAPE

PCl5 SF4 ICl3

AX2E3
LINEAR
XeF2
Valence-Shell Electron-Pair Repulsion 28
model AX E
A = Central Atom
z Y X = Bond
E = Lone pair

AX6 AX5E1 AX4E2

OCTAHEDRAL SQUARE PYRAMIDAL SQUARE PLANAR

SF6 BrF5 XeF4

AX3E3 AX2E2
T-SHAPED LINEAR
Valence-Shell Electron-Pair Repulsion 29
model

A = Central Atom
AXzE Y X = Bond
E = Lone pair
Valence-Shell Electron-Pair Repulsion 30
model

A = Central Atom
AXzE Y X = Bond
E = Lone pair
Formation of Bonds 31

Balance
between
attractive and
repulsive forces
Formation of Bonds 32

H-H 436 C-H 415 C=O 724 N-H 391 O-H 463 F-F 158

H-F 563 C-C 344 C=C 615 N-N 159 O-O 143 Cl-Cl 243

H-Cl 432 C-Cl 328 C=N 614 N-O 175 O-F 212 Br-Br 193

H-Br 366 C-N 292 N-F 270 S-H 368 I-I 151

H-I 299 C-O 350 C≡C 812 N-Cl 200 S-S266

C≡N 889 N=N 418

N≡N 946

Bond energies in kJ.mol-1

Intermolecular Forces 33

Intermolecular forces are the forces that are between molecules. And so that's different from an
intramolecular force, which is the force within a molecule.

• The type of intermolecular force in a substance, will depend on the nature of the molecule
• Polar molecules have an unequal distribution of charge, the molecule is said to be a dipole
• Non-polar moecules have an equal distribution of charge
• There are 6 types of intermolecular forces:

 Ion-dipole
 Ion induced-dipole I-D I-ID
 Dipole-dipole
 Dipole-induced dipole Van Der Waals Interaction
 Induced dipole-Induced dipole D-D
 Hydrogen bonds

D-ID
H-Bond