CHEM 357 Winter 2016-Workbook#02

L02 - A. Musgrove Richer

Chemical Bonding
Atoms, Electrons, and Orbitals:
Organic chemists are concerned with the electrons in atoms, and more importantly with the
electrons in molecules.
Electrons can be considered to have wave-like properties having discreet (quantized) energy
levels.
Relating these energy levels using a mathematical wave equation (Schrdinger equation)
gives a series of solutions called wave functions ( ):
o Only certain values of are allowed.
o Each corresponds to a certain energy.
o The probability of finding an electron at a particular point with respect to the nucleus
is given by 2.
o Each energy state corresponds to an orbital.
o Each orbital can only contain two electrons.
Each orbital is characterized by a unique set of quantum numbers.
The principal quantum number n is a whole number (integer) that specifies the shell and is
related to the energy of the orbital (n can = 1, 2, 3...etc.).
The angular momentum quantum number l is usually designated by a letter (s, p, d, f, etc.)
and describes the shape of the orbital (l can = 0, 1, 2...up to n-1 in value: s-orbital = 0, porbital = 1, d-orbital = 2, etc.).
The magnetic quantum number ml describes the spatial orientation of the orbital (values of ml
vary from +l to -l).
The spin quantum number ms describes the orientation of the two electrons in each orbital
(values of ms are either + or -).
The Pauli Exclusion Principle states that no two electrons in the same atom can have
the same set of four quantum numbers two electrons can occupy the same orbital
only when they have opposite spins - there is a maximum of two electrons per orbital.
Valence Bond Theory explains bond formation as arising from electron sharing through
overlap of two atomic orbitals.
o In order for a bond to form, the orbitals must have good overlap (orbitals should be
of similar size) and the phase of the orbitals (usually shown by color) must match.
Q1: Sketch the shapes of the 1s, 2s, 2px, 2py and 2pz orbitals:

Modified with permission from Dr. A. Causton, UC Chem

CHEM 357 Winter 2016-Workbook#02

L02 - A. Musgrove Richer

Q2: Sketch the overlap of these pairs of atomic orbitals and indicate whether a bond would form.
Assume that the internuclear axis lies along the z-axis, and y is up and down on the page.
1s 1s

2s 2pz

2s 2py

2pz 2pz

Electron Waves and Chemical Bonds:

Using Hydrogen as an example:
o A solution of the Schrdinger wave equation for hydrogen describes the shape of
the electron cloud surrounding hydrogen to be the spherical 1S shell
o A hydrogen atom consists of a positively charged proton in its nucleus and the
negatively charged electron shell (represented as + and in the diagram below).
_

+
A

+
B

o Between two hydrogen atoms there is an attraction between the positively

charged proton of atom A, and the negatively charged electrons of atom B (there
is also an attraction between the positively charged proton of atom B, and the
negatively charged electrons of atom A) these forces will draw the hydrogen
atoms together.

Modified with permission from Dr. A. Causton, UC Chem

CHEM 357 Winter 2016-Workbook#02

L02 - A. Musgrove Richer
o However, there is also a
repulsion between the
positively charged
proton of atom A, and
the positively charged
proton of atom B (there
is also an repulsion
between the negatively
charged electrons of
atom A, and the
negatively charged
electrons of atom B)
these forces will push
the hydrogen atoms
apart.
o These opposing forces balance a plot of potential energy versus inter-nuclear
distance gives the point at which the attractive forces are strongest (energy
minima) this distance is known as the bond length.
The bond length will depend on the size and type of orbitals involved. Larger atoms
(with larger atomic orbitals) will form longer bonds. The type of overlap ( or ) will also
affect the bond length.
Q3: Rank the following (single) bonds in order from longest to shortest.

1. C C

2. Cl Cl

3. F F

4. H H

5. O O

Hybridization Theory:
Combining atomic orbitals to form hybrid orbitals helps explain the 3-D geometries of molecules.
In hybridization theory, the atomic orbitals on a single atom are combined and averaged together to
form new atomic hybrid orbitals.
The names of these orbitals come from the number and type of orbitals used to form them:
o s + p = sp
o s + p + p = sp2
o s + p + p + p = sp3
Each hybridization has a characteristic geometry:
o sp linear
o sp2 trigonal planar
o sp3 tetrahedral
When determining the hybridization required for an atom, lone pairs and sigma bonds will
use hybrid orbitals, unoccupied orbitals and pi bonds will use unhybridized p orbitals.

Modified with permission from Dr. A. Causton, UC Chem

CHEM 357 Winter 2016-Workbook#02

L02 - A. Musgrove Richer

Q4: Using an orbital model, explain the hybridization & shapes of the following:

H
H

H
H

O
H

Q5: Determine the hybridization on each atom in ethane (C2H6). Sketch the orbital overlap diagram
for the ethane molecule.

Pi bonding involves the side-on overlap of adjacent unhybridized p-orbitals, where the orbital
overlap is above and below the bond axis, instead of along it (as for sigma bonds).

Q6: Draw the electronic configuration of carbon that can be used to explain the observed geometry
of carbon in (ethyne) acetylene (sp orbital hybridization).

Modified with permission from Dr. A. Causton, UC Chem

CHEM 357 Winter 2016-Workbook#02

L02 - A. Musgrove Richer

Q7: Sketch the bonding in acetylene (ethyne) using an orbital overlap diagram.

Effects of Resonance on Hybridization

When a molecule has different resonance structures possible, the observed geometry matches most
closely with the least-hybridized structure, so that is the hybridization we assign.
Note the three dimensional shape of the nitrogen atom in the amine vs. amide vs. nitro
functional groups by following the link:
http://www.chem.ucalgary.ca/courses/351/orgnom/functional/func.html
Q8: Complete the resonance structures and assign hybridizations to the N atoms in each of the
structures below.

Molecular Orbitals
Main Ideas:
o Electrons in a molecule occupy molecular orbitals (MOs) just as electrons in an
atom occupy atomic orbitals (AOs).
o Two electrons per MO, just as two electrons per AO.
o Express MOs as combinations of AOs.
Modified with permission from Dr. A. Causton, UC Chem

CHEM 357 Winter 2016-Workbook#02

L02 - A. Musgrove Richer

MO Picture of Bonding:
o Linear combination of atomic orbitals method expresses wave functions of
molecular orbitals as sums and differences of wave functions of atomic orbitals.
Q9: Use an energy level diagram to explain why He2 is not a stable, observable species.

Relative Stability of Molecules

The strength of a chemical bond can affect the properties of bond (and molecule).
Reaction Thermodynamics:
Heat (energy) is released during an exothermic reaction (Hr < 0).
Heat (energy) is absorbed during an endothermic reaction (Hr > 0).
Common Ways of Making Thermodynamic Comparisons between Molecules:
By comparing the potential energies of analogous molecules is how we can determine
the relative stability of a molecule (or conformation).
Hess Law
States that the overall energy transferred during a reaction is independent of the reaction
pathway
You can add together reactions (and their enthalpies) to determine the enthalpy of an overall
reaction
Often summarized using heats of formation: = . .
Q10: Calculate the heat of formation of hexane (Hf) from its constituent elements,
given that:
Hc for hexane = -4163 kJ/mol
Hc for carbon = -394 kJ/mol
Hc for hydrogen gas = -286 kJ/mol

Modified with permission from Dr. A. Causton, UC Chem

CHEM 357 Winter 2016-Workbook#02

L02 - A. Musgrove Richer

Q11: For the following 8-carbon constitutional isomers, predict which is thermodynamically
most stable, based on the heats of combustion given below each molecule. Sketch a
potential energy diagram.

cH: 5471 kJ/mol

5466 kJ/mol

5458 kJ/mol

5452 kJ/mol

Bond Strength Data:

C-H bond dissociation energies for some alkanes (kcal mol-1):
CH3-H
105
CH3CH2-H
98
(CH3)2CHCH2-H
98
CH3CH2CH2-H
98
(CH3)2CH-H
95
(CH3)3C-H
93

C-C bond dissociation energies for some alkanes (kcal mol-1):

CH3-CH3
90
CH3CH2-CH3
86
CH3CH2CH2-CH3
87
CH3CH2-CH2CH3
82
(CH3)2CH-CH3
86
(CH3)C-CH3
84

C-H bond dissociation energies (kcal mol-1):

CH3CH2-H
98
CH2=CHCH2-H
PhCH2-H
85
CH3C(=O)CH2-H

Modified with permission from Dr. A. Causton, UC Chem

85
92

CHEM 357 Winter 2016-Workbook#02

L02 - A. Musgrove Richer

C-H bond dissociation energies (kcal mol-1):

CH3CH2-H
98
H2C=CH-H
107
HCC-H
131
Q12: Use the above bond dissociation energies to explain the trend we previously saw in the
molecular stability for the molecules below.

Q13: Which bond is weakest in this molecule? Use orbital interactions to hypothesize why this
might be the case:

Modified with permission from Dr. A. Causton, UC Chem