CHEM 104 – Module 09 (Part 2) – ‘Lecture 19’ – Theories of Chemical Structure and Bonding
Top Hat Reading: Section 9.6 of Top Hat.
Top Hat Reading Assignment Questions: Q9.11 to Q9.18, due: Tuesday, March 25th at 11:59 pm.
Top Hat Homework Assignment for Module 09 Due: Friday, March 28th at 11:59 pm.
Video: Supplemental videos may be created. If so, they will be posted to our UR Courses website.
9.6 VSEPR Theory Shortcomings
Please describe one success of VSEPR theory, and one concern:
Valence Bond (VB) Theory
VB theory is based in quantum-mechanics and makes direct use of atomic orbitals.
What are the two requirements for a bond to occur under VB theory?
1. Valence orbitals on two atoms ______________________________________
2. Energy of the system _____________ as a result of overlap.
Bonding in Methane (CH4)
What is the electron configuration of carbon? ________________________
When using the orbitals on the left, only ______ of them have
unpaired electrons, so only _______ C-H bond are possible.
The predicted bond angle is 90 degrees.
The bond angle is actually ___________ degrees.
Page 1 of 11
CHEM 104 – Module 09 (Part 2) – ‘Lecture 19’ – Theories of Chemical Structure and Bonding
The theoretical prediction at this point is provided below (Image from: ‘Chemistry: A Molecular
Approach (4th Edition)’ by Nivaldo Tro.):
9.6.1 Hybridization
For CH4, using ‘standard’ atomic orbitals, we cannot create the correct number of bonds, nor can
we arrive at a correct bond angle.
To fix, it is postulated that valence atomic orbitals can hybridize (‘mix’) before bonding. One way
of doing this on the carbon atom in CH4 is to mix the 2s and 3 2p orbitals.
How many orbitals are obtained when mixing 1 2s orbital and 3 2p orbitals? _________
The mixing occurs so that the resulting hybrid orbitals point to the corners of a tetrahedron.
So, in VB theory, we can use ‘standard’ s-, p-, d-, and f-type orbitals, but ALSO hybrids.
CH4 with Hybridization
The 4 hybrid orbitals are degenerate and have an energy that is an average of the ‘standard’
orbitals.
Page 2 of 11
CHEM 104 – Module 09 (Part 2) – ‘Lecture 19’ – Theories of Chemical Structure and Bonding
Complete the following list of possible hybrid orbital types: sp, sp2, sp3, _____, ______.
The number of ‘standard’ atomic orbitals used equals the number of hybrid orbitals formed.
➢ one s orbital + three p orbitals = four sp3 hybrid orbitals.
Concept Check (in class)
How many sp3d hybrid orbitals result from the hybridization of s, p, and d orbitals?
Answer:
How many sp hybrid orbitals result from the hybridization of s and p orbitals?
Answer:
Determining the Hybridization State
It really depends on the number of electron domains.
Hybrid orbitals can be used for bonds (in CH4) or lone pairs (in NH3).
Page 3 of 11
CHEM 104 – Module 09 (Part 2) – ‘Lecture 19’ – Theories of Chemical Structure and Bonding
9.6.2 sp2 hybrid orbitals
So, the 4 sp3 hybrid orbitals can be used to create a tetrahedral electron domain geometry.
What electron domain geometry would three sp2 hybrid orbitals create? ___________________
Notice: there is one ‘leftover’ p orbital after hybridization. This can also be used to form bonds,
as described below.
𝝈 and 𝝅 bonds
Sigma (𝝈) bonds occur when the orbitals point along the direction connecting the two bonding
atoms and the orbitals overlap.
➢ Usually, a hybrid orbital from central atom to another hybrid orbital. Exception is
when hydrogen is one of the bonding atoms.
Pi (π) bond: orbitals are parallel to each other BUT perpendicular to the direction connecting the
two bonding atoms and the orbitals overlap.
➢ Occurs between unhybridized p and d orbitals
Which is stronger, a sigma bond or a pi bond?
Note: Between any two atoms, only 1 bond can be σ. Additional bonds between the 2 atoms are
π-type.
Page 4 of 11
CHEM 104 – Module 09 (Part 2) – ‘Lecture 19’ – Theories of Chemical Structure and Bonding
Note: if a 𝜋 bond is present, then the atoms cannot rotate around the bond.
9.6.3 sp Hybrid Orbitals
What electron domain geometry would two sp hybrid orbitals create? ___________________
Page 5 of 11
CHEM 104 – Module 09 (Part 2) – ‘Lecture 19’ – Theories of Chemical Structure and Bonding
Valence Bond Theory Method
1. Draw Lewis structure.
2. Use VSEPR theory to predict number of electron domains and geometry around atom(s)
of interest.
3. Select hybridization scheme that matches the electron domain geometry.
4. Sketch the atomic and hybrid orbitals on the atoms in the molecule, showing overlap
where appropriate.
5. Label bonds as σ or π.
Practice Question (in class)
Write the hybridization and bonding scheme for the central atom in HCN.
Practice Question #2 (in class)
Write the hybridization and bonding scheme for the central atom in CO2.
Page 6 of 11
CHEM 104 – Module 09 (Part 2) – ‘Lecture 19’ – Theories of Chemical Structure and Bonding
Bond Dissociation Energy (BDE)
BDE: energy required to break 1 mole of a given bond.
Is BDE always endothermic or exothermic? Does it release energy or require energy? What is
the corresponding sign of ∆𝑯?
BDE is _________thermic and so always ___________ energy.
The sign of ∆𝐻 is _____ ve.
A synonym of BDE is ‘bond enthalpy’
Chemical reactions involve breaking bonds in the reactants and creating bonds in the products.
°
∆𝐻rxn can be estimated by comparing the energy needed to break reactant bonds to the energy
released when making product bonds.
Table of Bond Enthalpies
Page 7 of 11
CHEM 104 – Module 09 (Part 2) – ‘Lecture 19’ – Theories of Chemical Structure and Bonding
Bond Enthalpy Trends
More shared electrons (higher ‘bond order’) generally gives a ____________ covalent bond.
A shorter covalent bond distance usually infers a _____________ bond.
Bond Enthalpies to Estimate ∆𝑯°𝐫𝐱𝐧
°
Can use bond enthalpies to estimate ∆𝐻rxn .
Bond breaking is always endothermic: ∆𝐻 is +ve, while bond making is always exothermic: ∆𝐻 is
°
−ve. The formular to calculate the ∆𝐻rxn from bond enthalpies is provided below:
°
∆𝐻rxn ≈ ∑(∆𝐻′s of bonds broken) − ∑(∆𝐻′s of bonds formed)
Example: Combustion of Methane (CH4)
Bonds broken
Bonds made:
Overall:
Page 8 of 11
CHEM 104 – Module 09 (Part 2) – ‘Lecture 19’ – Theories of Chemical Structure and Bonding
Practice Question (in class)
Use bond enthalpies to calculate ∆𝑯𝐫𝐱𝐧 for: N2 (g) + 3 H2 (g) → 2 NH3 (g)
9.6.4 sp3d Hybrid Orbitals
Five sp3d hybrid orbitals are formed when there are 5 electron domain geometries around
an atom and the resulting electron domain shape is trigonal bypiramidal.
Example: Phosphorus in PF5.
What is the electron configuration of phosphorus? ______________________
Starting from the ground state, complete the following to arrive at the hybridized state for
phosphorus:
Page 9 of 11
CHEM 104 – Module 09 (Part 2) – ‘Lecture 19’ – Theories of Chemical Structure and Bonding
The resulting geometry about the central phosphorus atom is provided in Figure 9.43 of the Top
Hat notes.
sp3d2 Hybrid Orbitals
Six sp3d2 hybrid orbitals are formed when there are 6 electron domain geometries around an
atom and the resulting electron domain shape is _________________________.
Example: Sulfur in SF6.
What is the electron configuration of sulfur? ______________________
Starting from the ground state, complete the following to arrive at the hybridized state for sulfur:
The resulting geometry for SF6 is provided below:
Page 10 of 11
CHEM 104 – Module 09 (Part 2) – ‘Lecture 19’ – Theories of Chemical Structure and Bonding
Practice Question (UR Courses)
Write the hybridization and bonding scheme for all atoms in XeF4. (Note: Lewis structure was
done in Module 08)
Page 11 of 11