Covalent Bonding: Orbitals: Chapter 14, J.Ren, 2021 1

Chapter 14
Covalent Bonding: Orbitals
Chapter 14, J.Ren, 2021 1

Localized Electron Model
• Description of the valence electron arrangemet:

Lewis structure (formal charge, resonance)
• Prediction of the geometry:

VSEPR model
• Description of the type of orbitals used for bonding:

Hybridization

The Structure of the Methane Molecule
(a) Lewis structure
(b) the tetrahedral molecular geometry

Valence orbitals on a free carbon atom
C valence:
2p (px, py, pz)
2s
Hybridization:
Mixing of the native atomic orbitals to form special
orbitals for bonding 4
Chapter 14, J.Ren, 2021
Hybridization:
Mixing of the native atomic orbitals to form special
orbitals for bonding
Mixing the carbon 2s and 2p orbitals
• Φ1 = (1/2)[(s) + (px) + (py) + (pz)]
• Φ2 = (1/2)[(s) + (px) - (py) - (pz)]
• Φ3 = (1/2)[(s) - (px) + (py) - (pz)]
• Φ4 = (1/2)[(s) - (px) - (py) + (pz)]

sp3 Hybridization
Native 2s and three 2p atomic orbitals of a free carbon
atome are combined to form a new set of four sp3 orbitals.
6
sp3 Hybridization
Native 2s and three 2p atomic orbitals of a free carbon
atome are combined to form a new set of four sp3 orbitals.
Energy level diagram
7
Formation of the Methane Molecule
σ-bond: “head to head” orbital overlap

Can free rotation

The sp3 Hybridization and the Ammonia Molecule
N valence: 2s2, 2p3
9
The Structure of the Ethylene Molecule
Trigonal planar
sp2 Hybridization
The hybridization of the s, px, and py atomic orbitals results in
the formation of three sp2 orbitals centered in the xy plane.
11
sp2 Hybridization
The hybridization of the s, px, and py atomic orbitals results in
the formation of three sp2 orbitals centered in the xy plane.
2p
2p
sp2
2s
Carbon atom Hybridization
12
Formation of the Ethylene Molecule
(a) The orbitals used to form the bonds in ethylene.
(b) The Lewis structure for ethylene.
π-bond: side-to-side orbital overlap

σ-bond
Cannot free-rotation
13
Examples: sp2 Hybridization
B valence: 2s2, 2p1
Trigonal planar

The Structure of the Acetylene Molecule
Linear

sp Hybridization
When one s orbital and one p orbital are hybridized, a set of two
sp orbitals oriented at 180 degrees results.
16
sp Hybridization
When one s orbital and one p orbital are hybridized, a set of two
sp orbitals oriented at 180 degrees results.
2p
2p
sp
2s
Carbon atom Hybridization
17
Formation of the Acetylene Molecule

Examples: sp Hybridization

Examples: sp Hybridization

The Structure of Phosphorus Pentachloride
Trigonal bipyramidal

dsp3 Hybridization
The orbitals used to form
A set of dsp3 hybrid
the bonds in the PCl5
orbitals on a
molecule
phosphorous atom
Trigonal bipyramidal
22
Example: dsp3 Hybridization

d2sp3 Hybridization
The Structure of An octahedral set of d2sp3
Sulfur Hexafluoride orbitals on a sulfur atom
Octahedral 24
Example: d2sp3 hybridization and XeF4

The relationship among the number of effective
pairs, their spatial arrangement, and the hybrid
orbital set required

Examples: Hybridization and Molecular Structure
For the following molecule and ions:
a) Draw the Lewis structures with proper geometry and show all non-
zero formal charges and all unshared electron pairs. Indicate the
approximate bond angles
b) Tell whether the molecular or ion would be polar or non-polar
c) Tell the expected hybridization for each atom except hydrogen.
CO, BF3, BF4¯, HCOH, SO32-
SF4, AsF5, IF5, XeCl2, H3N-BH3, F3S-SF
POCl3, PCl2¯, ClO4¯, NO2¯ SeO2, ICl3
27
In-Class: Hybridization and Molecular Structure
a) Draw the Lewis structures with proper geometry and show all non-zero
formal charges and all unshared electron pairs. Indicate the approximate
bond angles
b) Tell whether the molecular or ion would be polar or non-polar
c) Tell the expected hybridization for each atom except hydrogen.
SO32- SF4, AsF5, IF5, XeCl2,
F3S-SF POCl3 PCl2¯, ClO4¯, NO2¯
SeO2, ICl3
28
The Molecular Orbital (MO) Model
• The MO model assumes that the molecular orbitals
are constructed using a set of atomic orbitals via
“linear combination”.
MO1 = AO1 + AO2
MO2 = AO1 - AO2
• Orbitals are conserved. The number of AOs always
give the same number of MOs.
• No hybridization process is involved.
• All electrons in an atom are involved in the
formation of the molecular orbitals.

The combination of hydrogen 1s atomic
orbitals to form H2 MOs
Electron configuration for H2: (σ1s)2
Bond order = number of bonding electrons – number of antibonding electrons

2
Bond order = 1 30
The MO energy-level The MO energy-level diagram
diagram for the He2 molecule for the He2+ ion.
He2: (σ1s)2(σ1s*)2 He2: (σ1s)2(σ1s*)1
Bond order = 0 Bond order = 0.5

He2 Predicted to be unstable He2+ Predicted to be stable
31
The relative sizes of the lithium 1s and 2s atomic
orbitals
• To participate in molecular orbitals, atomic orbitals

must overlap in space.
• Only the valence orbitals contribute significantly to
the MOs. 32
The MO energy-level diagram for the Li2 molecule
Bond order = 1

The three mutually perpendicular 2p orbitals on
two adjacent boron atoms.
σ-bond
π-bond π-bond

The two p oribitals on the boron atom that overlap head-on
combine to form bonding and antibonding orbitals.

Diagram 1 Diagram 2
MO energy-level diagram for the B2 MO energy-level diagram for the B2
Which
one is
correct?
B2: (σ2s)2(σ2s*)2(σ2p)2 B2: (σ2s)2(σ2s*)2(π2p)2

Bond order = 1 Bond order = 1 36
Paramagnetism and Diamagnetism
Paramagnetism causes the substance to be
attracted to the inducing magnetic field.
Paramagnetism is associated with unpaired

electrons.
Diamagnetism causes the substance to be repelled

from the inducing magnetic field.
Diamagnetism is associated with paired electrons.

An apparatus used to measure the paramagnetism
of a sample
Appear to be “heavier”
Experiment shows that
B2 is paramagnetic
38
The predicted MO energy- The correct MO energy-level
level diagram for the B2 diagram for the B2 molecule.
B2: (σ2s)2(σ2s*)2(σ2p)2 B2: (σ2s)2(σ2s*)2(π2p)2

Diamagnetic Bond order = 1 Paramagnetic 39
The MO energy-level diagrams, bond orders, bond energies, and bond
lengths for the diatomic molecules, B2 through F2.
Li2, Be2, B2, C2, N2

Have the same order
of energy levels
O2, F2, (Ne2)

Have the same order
of energy levels

40
Chapter 14, J. Ren
The MO energy-level diagram for the O2 and N2
O2 is Paramagnetic N2 is Diamagnetic
O2: (σ2s)2(σ2s*)2(σ2p)2 (π2p)4(π2p*)2 N2: (σ2s)2(σ2s*)2(π2p)4(σ2p)2

Bond order = 2 Bond order = 3 41
When liquid oxygen is poured into the space between the poles
of a strong magnet, it remains there until it boils away.
Source: Donald Clegg

O2 is Paramagnetic
While liquid nitrogen flows through the poles of the magnet.

N2 is Diamagnetic
http://www.youtube.com/watch?v=KcGEev8qulA
42
Examples: MO for homonuclear molecules
a) Draw the energy level diagram
b) Give the electron configuration
c) Calculate the bond order
d) Tell whether each species is diamagnetic or
paramagnetic.
O2, O2+, O2¯, Ne2+, N2+, P2 , P2¯

The MO energy-level diagram for the NO molecule
Molecules contain atoms

adjacent to each other in the
periodic table can be treated
as homonuclear molecules.
NO can be treated as N2
NO: 11 valence electrons
Bond order = 2.5

paramagnetic

Heteronuclear molecules with two very different atoms
A partial MO energy-level The electron probability
diagram for the HF distribution in the bonding MO
molecule of the HF molecule

Combining the Localized Electron Model and
Molecular Orbital Model
• Localized electron (LE) model including Lewis structure,
VSEPR model, resonance, and hybridization
• The LE model is simple, but it does not describe molecules
with multiple bonds clearly
• The MO model is too complicated for molecules with many
atoms.
A practical approach for molecules with multiple bonds:

• Use LE model to describe the σ-bonds
• Use MO model to describe the π-bonds

The resonance structures for NO3- (LE Model)
(-) (-)
(-) (-) (-) (-)
The LE model is simple, but it does not describe

molecules with multiple bonds clearly

Combining the LE Model and the MO Model
for NO3- Ion
Use LE model to describe the σ-bond
Use MO model to describe the π-bond
48
The resonance structures for Benzene (LE Model)
The benzene molecule consists of a ring of six
carbon atoms with one hydrogen atom bound to
each carbon; all atoms are in the same plane.

Combining the LE Model and the MO Model
for Benzene
The σ bonding The π system in benzene is formed
system in benzene by combining the six p orbitals

Introduction to Molecular Spectroscopy
Electronic Vibrational Rotational NMR
spectroscopy spectroscopy spectroscopy spectroscopy
UV-Vis IR region Microwave Radio wave
region region region

Electronic Spectroscopy
Involves electron transition between energy levels
The molecular orbital diagram for the ground state and the first excited
state of NO+
UV light
Ground state First excited state

Electronic Spectroscopy
The molecular The electronic absorption
structure of spectrum of beta-carotene.
beta-carotene
Absorb blue-violet light
Reflect red-orange light
53
Vibrational Spectroscopy (IR)
Describe vibrational properties of a molecule
Classical Model: A bond is like a spring
1 2 1 2
1 1
1 2
-1
54
Vibrational Spectroscopy (IR)
Quantum Mechanical Model
Vibrational energy is quantized
Vibrational quantum number 55

Examples: Application of vibrational spectroscopy
The IR spectrum of gaseous HCl shows the v = 0
to v = 1 transition at 2885 cm-1. Calculate the
vibrational force constant for HCl.
Unit conversion: J = kg m2/s2

Js = kg m2/s
1 atomic mass unit = 1.661 x 10-27 kg
Ans: 4.80 x 102 kg s-2 (or J m-2)

IR Spectrometer
Copied from website

Vibrational Spectroscopy
The three fundamental vibrations for sulfur dioxide
1152 cm-1 1362 cm-1 518 cm-1

58
IR Spectrum
1152 cm-1
1362 cm-1 518 cm-1

Vibrational Spectroscopy O
IR Spectrum CH3CH2CH2CH2
C
CH2CH3
Chapter 14, 2,
Chapter J.Ren,
J. Ren2021 60 60
Nuclear Magnetic Resonance (NMR)
Representations of the two spin states of the
proton interacting
62
Principle of NMR
Certain nuclei have allowed spin states
1
1 13 19 31 Spin quantum number: I =
H ( C, F, P) 2
Two spin states:

1 _ 1
+
N 2 2
H+ S  
RF
E = hv
 
E E Int
 
chemical shift (
Bo Bo
External magnetic field External magnetic field 63
NMR Spectrometer and NMR Spectrum
64

NMR Spectrum and Chemical Shift
CH3
H3C Si CH3
CH3
TMS
Internal Standard
65
Chemical Shift, ppm Chapter 14, J.Ren, 2021
The molecular
The expected NMR
structure of
spectrum for bromoethane
bromoethane
a
b
• Magnetic equivalent protons produce one signal

• Magnetic non-equivalent protons produce different signals
• The areas of the signals are proportional to the number of

equivalent protons Chapter 14, J.Ren, 2021 66
Example: NMR Spectrum

NMR Signal Splitting
The spin of proton Hy can be "up" or "down"
Hx
• Hy splits the signal of Hx into a doublet
The splitting follows the (n + 1) rule, where n represent

the number of adjacent neighboring protons
68
NMR Signal Splitting: (n + 1) rule
The two Hy protons split the The four Hy protons split the
signal of Hx into 3 peaks signal of Hx into 4 peaks
(triplet) (quartet).
Hx Hx
69
The NMR spectrum of CH3CH2Br (bromoethane)
with TMS reference

The NMR spectrum of 2-butanone molecule
• Spin-spin coupling (signal splitting) is observed for hydrogens

that are separated by less than three bonds
Match the molecules to the NMR spectrum
CHCl2CH2Cl or CH3CH2Cl

A technician speaks to a A colored Magnetic
patient before he is moved Resonance Imaging (MRI)
into the cavity of a magnetic scan through a human head,
resonance imaging (MRI) showing a healthy brain in
machine. side view.

3/01/17
End of Chapter 14

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Chapter 14

Covalent Bonding: Orbitals

Chapter 14, J.Ren, 2021 1

• Description of the valence electron arrangemet:

• Prediction of the geometry:

• Description of the type of orbitals used for bonding:

Chapter 14, J.Ren, 2021 2

Chapter 14, J.Ren, 2021 3

Chapter 14, J.Ren, 2021 5

Energy level diagram

σ-bond: “head to head” orbital overlap

Chapter 14, J.Ren, 2021 8

Energy level diagram

Carbon atom Hybridization

π-bond: side-to-side orbital overlap

Chapter 14, J.Ren, 2021 14

Chapter 14, J.Ren, 2021 15

Carbon atom Hybridization

Chapter 14, J.Ren, 2021 18

Chapter 14, J.Ren, 2021 19

Chapter 14, J.Ren, 2021 20

Chapter 14, J.Ren, 2021 21

Chapter 14, J.Ren, 2021 23

Chapter 14, J.Ren, 2021 25

Chapter 14, J.Ren, 2021 26

CO, BF3, BF4¯, HCOH, SO32-

SF4, AsF5, IF5, XeCl2, H3N-BH3, F3S-SF

POCl3, PCl2¯, ClO4¯, NO2¯ SeO2, ICl3

SO32- SF4, AsF5, IF5, XeCl2,

F3S-SF POCl3 PCl2¯, ClO4¯, NO2¯

Chapter 14, J.Ren, 2021 29

Electron configuration for H2: (σ1s)2

Bond order = number of bonding electrons – number of antibonding electrons

He2: (σ1s)2(σ1s*)2 He2: (σ1s)2(σ1s*)1

Bond order = 0 Bond order = 0.5

• To participate in molecular orbitals, atomic orbitals

Chapter 14, J.Ren, 2021 33

Chapter 14, J.Ren, 2021 34

Chapter 14, J.Ren, 2021 35

B2: (σ2s)2(σ2s*)2(σ2p)2 B2: (σ2s)2(σ2s*)2(π2p)2

Paramagnetism is associated with unpaired

Diamagnetism causes the substance to be repelled

Diamagnetism is associated with paired electrons.

B2: (σ2s)2(σ2s*)2(σ2p)2 B2: (σ2s)2(σ2s*)2(π2p)2

Li2, Be2, B2, C2, N2

O2, F2, (Ne2)

Chapter 14, J.Ren, 2021 40

O2: (σ2s)2(σ2s*)2(σ2p)2 (π2p)4(π2p*)2 N2: (σ2s)2(σ2s*)2(π2p)4(σ2p)2

Source: Donald Clegg

While liquid nitrogen flows through the poles of the magnet.

O2, O2+, O2¯, Ne2+, N2+, P2 , P2¯

Chapter 14, J.Ren, 2021 43

Molecules contain atoms

NO: 11 valence electrons

Bond order = 2.5

Chapter 14, J.Ren, 2021 44

Chapter 14, J.Ren, 2021 45

He2: (σ1s)2(σ1s)2 He2: (σ1s)2(σ1s)1

B2: (σ2s)2(σ2s)2(σ2p)2 B2: (σ2s)2(σ2s)2(π2p)2

B2: (σ2s)2(σ2s)2(σ2p)2 B2: (σ2s)2(σ2s)2(π2p)2

O2: (σ2s)2(σ2s)2(σ2p)2 (π2p)4(π2p)2 N2: (σ2s)2(σ2s*)2(π2p)4(σ2p)2