)
GSI: Christine Chang (chang@berkeley.edu)
Office Hours: (Dead Week) Tuesday 4:30 – 5:30 pm and Thursday 3:00 – 4:00 pm
Some Related Notes
Electronegativity
Recall that:
‐ Ionization energy: the energy needed to remove an electron from the atom
‐ Electron affinity: the negative of the energy released when an electron is gained by the
atom
‐ Electronegativity: the tendency of the atom to “hold” electrons closer to itself
(Defined mathematically as EN =
IL+LA
2
)
When two atoms in a molecule have differing electronegativities, a permanent dipole moment
occurs. The more electronegative atom attracts electrons more than the less electronegative atom,
creating partial negative and positive charges in the molecule.
Quantum Mechanics
Heisenberg Uncertainty
∆E∆t ¸
ħ
2
∆x∆p ¸
ħ
2
What is Quantum Mechanics?
‐ Quantum mechanics is physics at the “microscopic scale.”
o As a system gets larger, it behaves more classically. For instance, a baseball
exhibits relatively little quantum mechanical behavior.
‐ Waveparticle duality: electromagnetic waves can act as particles, and particles of matter
can act as waves.
‐ Energies of particles can be discrete, or quantized.
‐ The wavefunction Ψ is the most complete description that can be given to a physical
system.
CHEM 4AL Section 102 (Monday 26pm)
GSI: Christine Chang (chang@berkeley.edu)
Office Hours: (Dead Week) Tuesday 4:30 – 5:30 pm and Thursday 3:00 – 4:00 pm
‐ Born postulate: The probability of finding a particle described by the wavefunction Ψ is:
JP(x, t) = V
∗
VJx = V
2
Jx
with the normalization condition
1 = ] V
∗
VJx
«
«
satisfied.
Schrödinger Equation
Operators
‐ What is an operator?
A
`
¡(x) = g(x)
o Some examples of operators:
x´¡(x) = x ∙ ¡(x)
x´
2
¡(x) = x ∙ x ∙ ¡(x)
Ð
´
(x)¡(x) =
ð
ðx
¡(x)
‐ We can define the eigenvalue of operator A
`
as:
A
`
¡
n
(x) = z
n
¡
n
(x)
Understanding the Schrödinger Equation
‐ We use the Schrödinger equation to describe a quantum system!
‐ How do we get the Schrödinger equation?
E
´
V = EV
We want E (total energy) = T (kinetic energy) + V (potential energy).
For the electron, KE =
1
2
m:
2
=
p
2
2m
.
PE = Coulombic forces between two electrons
_
ħ
2
2m
_
o
2
ox
2
+
o
2
oy
2
+
o
2
oz
2
_ 
c
2
4ne
0
r
_V = EV
‐ The Schrödinger equation predicts the quantization of energy!
o E is the energy eigenstate of the Hamiltonian.
CHEM 4AL Section 102 (Monday 26pm)
GSI: Christine Chang (chang@berkeley.edu)
Office Hours: (Dead Week) Tuesday 4:30 – 5:30 pm and Thursday 3:00 – 4:00 pm
Waves and Orbitals
Waves
‐ The state of a wavelike particle can be described using a wavefunction (Ψ).
‐ Waves have nodes, points at which the wavefunction is equal to zero.
o More nodes = higher energy!
‐ The possible location of an electron in an atom is described by orbitals, which are three
dimensional waves.
o Threedimensional waves can have radial nodes and/or angular nodes.
o In an atom, we name orbitals according to the following rules:
n = (total # of nodes) + 1
l = # angular nodes
(0, 1, 2, …) = (s, p, d, …)
m
I
= l, l +1, …, l +1, l
m
s
= ±1
Increasing energy
Increasing #
nodes
0
1
2
3
etc.
CHEM 4AL Section 102 (Monday 26pm)
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Office Hours: (Dead Week) Tuesday 4:30 – 5:30 pm and Thursday 3:00 – 4:00 pm
Quantum Numbers
We can describe an orbital using quantum numbers. These are listed in the table below.
Quantum
Number
Name Value
n Principal quantum number (# radial nodes) + (# angular nodes) + 1
l Angular quantum number (# angular nodes) + 1
m
I
Magnetic quantum number {l, …, 0, …, l }
m
s
Spin quantum number ±½
Wavefunctions and Nodes
Recall that Ψ depends on r, θ, and φ. Separating Ψ into radial and angular parts:
V(r, 0, ç) = R(r) ∙ ¥(0, ç)
‐ At a node, Ψ = 0.
‐ At a radial node, R = 0.
‐ At an angular node, Y = 0.
Electron Density Diagrams
Where in the orbital will we be able to find an electron? To deduce this, we use electron density
diagrams. Say the electron can be described by the wavefunction Ψ. We can then describe the
probability of finding that electron in an orbital by looking at the value of Ψ
2
for a given value of
r.
How do we draw these diagrams? In class, we covered both Ψ
2
and r
2
Ψ
2
.
Shielding
What causes shielding?
‐ Electrons carry a negative charge, and thus electrons repel each other.
‐ For multielectron atoms, Z
eff
< Z.
CHEM 4AL Section 102 (Monday 26pm)
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Office Hours: (Dead Week) Tuesday 4:30 – 5:30 pm and Thursday 3:00 – 4:00 pm
Penetration
‐ In a multielectron system, the electron density of the outer electron can penetrate the
electron density of the inner electron.
‐ The 2s orbital penetrates the 1s better than the 2p orbital does. Thus, the 2s orbital is of a
lower energy than the 2p orbital.
‐ Similarly, for 1s penetration, 3s > 3p > 3d, etc.
We can use these ideas to develop a better understanding of the periodic table.
The Periodic Table
Orbitals and How Electrons Occupy Them
We fill orbitals with electrons starting with the lowest energy orbitals.
(This is called the Aufbau Principle.)
When filling orbitals with electrons, these rules are important:
‐ Pauli Exclusion Principle: Two electrons with the same spin cannot occupy the same
quantum state.
‐ Hund’s Rule: Electrons will singly fill orbitals before doubly occupying them.
Exceptions: Cr, Nb, Mo
Periodic Trends
Trends in the various properties of elements can be observed on the periodic table. Some
important trends include:
‐ Atomic radius: the size of the atom
‐ Ionization energy: the energy needed to remove an electron from the atom
‐ Electron affinity: the negative of the energy released when an electron is gained by the
atom
CHEM 4AL Section 102 (Monday 26pm)
GSI: Christine Chang (chang@berkeley.edu)
Office Hours: (Dead Week) Tuesday 4:30 – 5:30 pm and Thursday 3:00 – 4:00 pm
‐ Electronegativity: the tendency of the atom to “hold” electrons closer to itself
(Defined mathematically as EN =
IL+LA
2
)
Resonance Structures
What makes a Lewis structure “more significant”?
1. Satisfies the octet rule.
Elements with d valence orbitals can accommodate more than an octet.
2. Maximizes the number of covalent bonds.
3. Formal charges are minimized and logically distributed.
Electronegative atoms favor negative, not positive, formal charges.
Opposite formal charges should be as close together as possible, while samesign
formal charges should be as far away as possible.
How do we draw Lewis structures?
1. Count the number of valence electrons in the molecule.
For neutral atoms: use the periodic table. (i.e. C = 4 e

, P = 5 e

)
For each positive charge, subtract an electron from the count.
For each negative charge, add an electron to the count.
2. Choose a central atom.
3. Attach the other atoms to the central atom. Try to use the guidelines for creating “more
significant” Lewis structures.
Dots (electrons), lines/wedges/dashes (bonds)
4. Assign and clearly label formal charges on structures.
Counting formal charges: (Group #) – (# bonds + # electrons)
i.e.
N: Group 5 – (2 e

+3 bonds) = 0
3H: Group 1 – (1 bond) = 0
CHEM 4AL Section 102 (Monday 26pm)
GSI: Christine Chang (chang@berkeley.edu)
Office Hours: (Dead Week) Tuesday 4:30 – 5:30 pm and Thursday 3:00 – 4:00 pm
Oxoacid strength
‐ What is a conjugate acid/base?
Acid + Base → Conjugate Base + Conjugate Acid
‐ To examine the acid strength of an oxoacid (contains two or more oxygens), we can look
at the resonance stabilization of the conjugate base.
‐ Question: which oxoacid is the most stable, H
2
SO
4
, H
3
PO
4
, or HClO
4
?
Valence Shell Electron Repulsion (VSEPR) Theory
What is VSEPR?
‐ VSEPR theory is a predictive theory for the geometric shapes molecules will most likely
assume based on the number of bonds and lone electron pairs which are formed on
atoms.
o Electronelectron repulsion: Bonds/lone pairs will want to be as far away from each
other as possible; hence, the geometric configurations which allow for this can be
used to predict molecular geometry.
‐ Steric number = (# atoms bonded to central atom) + (# lone e

pairs on the central atom)
‐ Lone pairs repel electrons more strongly than bonded electrons do, so they push the
angles in atoms.
Using VSEPR to Predict Molecular Geometries
1. Draw the Lewis structures of the molecule. We will use the most significant structure as the
basis for the Lewis structure.
2. Assign the steric number to the structure.
3. Arrange the bonded atoms and lone pairs based on the steric number.
4. Deduce the molecular geometry.
Alternatively, you can use AXE notation. (A = central atom, X = bonded atom, E = electron pair.)
CHEM 4AL Section 102 (Monday 26pm)
GSI: Christine Chang (chang@berkeley.edu)
Office Hours: (Dead Week) Tuesday 4:30 – 5:30 pm and Thursday 3:00 – 4:00 pm
Introduction to Molecular Orbital (MO) Theory
Definition: Molecular orbital theory is a method for determining molecular structure. Instead of
placing the electrons in bonds between two nuclei, we treat the electrons as existing around and
being influenced by both of the nuclei equally.
i.e.
vs.
Lewis structures Molecular Orbitals
(In class we used the term MOLCAO: molecular orbital linear combination of atomic orbitals.)
Conceptually, think of what happens when two atoms approach each other.
→ Overall, MO theory gives us a more descriptive picture of electron bonding and
distribution than Lewis structures do!
Vocabulary:
Bonu 0iuei =
(# oI bondIng cIcctrons)  (# oI antIbondIng cIcctrons)
2
Paramagnetic molecules have unpaired electrons in their molecular orbitals.
Diamagnetic molecules have all paired electrons in their molecular orbitals.
The Highest Occupied Molecular Orbital (HOMO) is the molecular orbital with the
highest energy which still contains electrons.
The Lowest Unoccupied Molecular Orbital (LUMO) is the molecular orbital with the
lowest energy which is absent of electrons.
Molecular Orbital (MO) Diagrams
How do we know how to label molecular orbitals?
→ Recall that the interactions between s orbitals result in σ MOs.
In σ MOs, the atomic orbitals directly overlap one another in a headon approach.
In π MOs, the atomic orbitals interact via sideon bonding interactions.
CHEM 4AL Section 102 (Monday 26pm)
GSI: Christine Chang (chang@berkeley.edu)
Office Hours: (Dead Week) Tuesday 4:30 – 5:30 pm and Thursday 3:00 – 4:00 pm
Remember that Group 6 and 7 elements are exceptions to the typical energetic ordering of
molecular orbitals!
Question: How do molecular orbital diagrams look like for bonding between two different
molecules?
Before, we looked at homonuclear molecules. We will now move onto heteronuclear molecules.
First, we need to understand the factors governing how and when different atomic orbitals will
interact.
1. The symmetries of the interacting atomic orbitals must be the same.
We are creating more constructive interference, but also more destructive interference,
and these ultimately cancel out and we will see no overall bonding or antibonding
interactions. These are called nonbonding orbitals.
2. When ordering the atomic orbitals by energy, the more electronegative atoms will
have orbitals lower in energy.
This is because the energy of valence electron orbitals is obtained from the negative of the
ionization energy.
3. The absolute energies of the atomic orbitals must be similar enough for interaction.
To illustrate these points, we can look at the MO diagram for hydrogen fluoride.
Summary: Drawing Molecular Orbital Diagrams
1. Draw the energy axis.
2. Position the valence atomic orbitals in order of their energy and fill them with electrons.
3. Determine whether either of your atoms is within Groups 6/7 on the periodic table (O, F
columns). If so, we will have to consider the exception case.
4. Draw the molecular orbitals in order of energy.
5. Fill the molecular orbitals with electrons using Hund’s Rule and the Pauli Exclusion
Principle.
CHEM 4AL Section 102 (Monday 26pm)
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Office Hours: (Dead Week) Tuesday 4:30 – 5:30 pm and Thursday 3:00 – 4:00 pm
More Uses for Molecular Orbital Diagrams
Molecular orbitals can also give us useful information about molecules, particularly about their
bond length and bond energy.
Bond Length: By inspection, we can estimate the bond lengths of some atoms based upon
periodic trends. The more electronegative an atom is, the more closely it holds its electrons, and
the smaller its atomic radius. Thus, the bond length is shorter.
Using MO diagrams, we can also look at bond length by calculating the bond order. A higher
bond order signifies a stronger bond, which results in a shorter bond length.
Bond Energy: A stronger bond requires more energy to break. Molecules with shorter bond
lengths will have a stronger bonding interaction. Thus, in general, the bond energy is greater.
Hybridization
Definition: Hybridization is the mixing of atomic orbitals into new, hybrid orbitals for the
description of bonding in a molecule. The hybrid orbitals reflect the atomic orbitals which
contribute to the hybrid orbital, and their relative contributions.
i.e. sp orbitals result from the hybridization of one s and one p orbital, and thus have a 1:1 s:p
contribution. (sp
2
= 1:2, sp
3
= 1:3)
Question: Why is hybridization useful?
Example 1. CH
4
Let’s look at the “molecular orbital diagram”:
2p
2s
1s
C
1s
H
+
4
CHEM 4AL Section 102 (Monday 26pm)
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Notice how there are only two unpaired electrons. Thus, we would expect two covalent bonds to
form, resulting in CH
2
, and meaning CH
4
is an unstable molecule.
But in reality, the opposite is observed! (CH
4
is stable, and CH
2
is very unstable)
How can we explain the existence of CH
4
?
First, the 2s electron is excited.
Then, the 2s and 2p orbitals hybridize into four sp
3
orbitals.
The four sp
3
orbitals can then bond to the four H atoms to form covalent bonds which are
identical in length and strength.
This is what we observe!
How to Hybridize Orbitals
1. Use VSEPR to determine the geometry of the molecule.
2. Determine the hybridization at each atom (sp
3
, sp
2
, sp).
3. Use unused porbitals to form π bonds.
CHEM 4AL Section 102 (Monday 26pm)
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Office Hours: (Dead Week) Tuesday 4:30 – 5:30 pm and Thursday 3:00 – 4:00 pm
Delocalized πSystems
Aromaticity occurs when electrons are delocalized over a πsystem, and lend stability to a
molecule. Aromatic molecules have 4n+2 πelectrons. Antiaromatic molecules have 4n π
electrons.
Consider benzene:
We can illustrate the orbitals of benzene using a Frost circle.
How to Draw Frost Circles:
1. Draw the polygon with its point facing downwards, and draw a circle around the polygon.
2. Draw an energy axis. At each polygonal vertex, draw a line to represent a π molecular
orbital.
3. Fill the diagram with the correct number of electrons. (For benzene, there are 6.)
Introduction to Spectroscopy
What is Spectroscopy?
Spectroscopy is the interaction of electromagnetic radiation with atoms and molecules, used to
elucidate information about atomic and molecular structure.
When microwave radiation is absorbed, transitions between rotational energy levels are
generally observed.
CHEM 4AL Section 102 (Monday 26pm)
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When infrared radiation is absorbed, transitions between rotational & vibrational
energy levels are observed.
When visible/ultraviolet radiation is absorbed, transitions between electronic,
vibrational, & rotational energy levels are observed.
Thus, we often describe these types of spectroscopy as rotational, vibrational, and
electronic spectroscopy, respectively.
The absorption/emission of radiation occurs when a change in the electric field is induced. This is
important for our later discussion of selection rules.
The energy of the absorbed radiation is:
∆E = E
uppc¡
E
Iowc¡
= bv =
bc
z
= bcv¯
The following table illustrates the different types of spectroscopy and the kind of information
about the molecule that each method reveals.
Selection Rules
In order for a rotational transition to be allowed:
1) The molecule must have a permanent dipole moment which does not lie along the main
rotation axis.
A permanent dipole moment occurs when a pair of nearby electric charges has
charges of equal magnitude but opposite sign.
A temporary dipole moment includes weaker phenomena such as induced dipoles
and London dispersion forces.
CHEM 4AL Section 102 (Monday 26pm)
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2) ∆[ = _1
3) ∆H = u
In order for a vibrational transition to be allowed:
1) The molecule’s dipole moment must vary during a vibration.
For instance, stretching bond length will have an effect on the dipole moment
(p = qR).
Bending bonds to alter the dipole moment can also change the dipole moment.
The total number of vibrational modes a molecule will have is equal to 3N – 5 for
linear molecules, or 3N – 6 otherwise.
N is the number of atoms in the molecule.
3N degrees of freedom, minus 3 translational, minus 3 rotational (2 for
linear molecules)
2) ∆: = _1
Rotational Spectroscopy
We can model rotational spectroscopy quantum mechanically using the rigid rotor
approximation.
Rigid rotor:
The solution to the Schrödinger equation for the rigid rotor is
E
]
=
b
2
8n
2
I
[ ([ + 1)
J = 0, 1, 2, …
I is the moment of inertia.
CHEM 4AL Section 102 (Monday 26pm)
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(I = pR
2
=
m
1
m
2
m
1
+m
2
R
2
)
When electromagnetic radiation is being absorbed, the molecule goes from quantum state J to J +
1. The energy difference between these two states can be written as
∆E = E
]+1
E
]
=
b
2
8n
2
I
([ +1)([ +2) [([ +1)]
=
b
2
4n
2
I
([ +1)
Using E = hν, we can calculate the frequencies at which the absorption transitions occur:
v =
b
4n
2
I
([ +1)
Each energy level has a degeneracy given by
g = 2[ +1
In rotational spectroscopy, according to the rigid rotor model, transitions must occur between
adjacent levels (recall the selection rules).
Note the this model results in evenly spaced lines, separated by distances of 2B, where
CHEM 4AL Section 102 (Monday 26pm)
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B
¯
=
b
8n
2
cI
Note that B =
h
8n
2
I
. This gives you B in units of Hz, or frequency. B
¯
is in units of wavenumbers
(cm
1
).
Vibrational Spectroscopy
We can model vibrational spectroscopy quantum mechanically using the harmonic oscillator
approximation.
The solution to the Schrödinger equation for the harmonic oscillator is
E
¡
=
b
2n
_
k
p
]
1
2
,
_: +
1
2
]
: = u, 1, 2, …
k is the spring (or force) constant, i.e. bond
strength
** Often, [
k
µ
¸
1
2
,
is abbreviated as ω, AKA
the angular frequency
æ = 2nv, where ν is the oscillation
frequency (v = :! Nu vs. V)
E
¡
=
bæ
2n
_: +
1
2
] = bv _: +
1
2
]
When electromagnetic radiation is being absorbed, the molecule goes from quantum state v to v
+ 1. The energy difference between these two states can be written as
∆E = E
¡+1
E
¡
=
bæ
2n
__: +
S
2
] _: +
1
2
]_
=
bæ
2n
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This satisfies the condition E = hν, with ν equal to
: =
æ
2n
The degeneracy of each state is given by
g =
(N +: 1)!
:!
BeerLambert Law
The BeerLambert Law states that
A = log
10
_
I
sumpIc
I
¡c]
_ = log
10
(I) = c e l
To find the relative absorbances of two different samples, you can take the ratio of the two
absorbances.
A
n
A
m
=
log
10
(I
n
)
log
10
(I
m
)
Energy Potentials
Recall that we use the potential well for a harmonic oscillator as an approximation for an
intermolecular potential energy curve.
CHEM 4AL Section 102 (Monday 26pm)
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Another model for the intermolecular potential energy well is a Morse potential,
Electronic Spectroscopy
Molecules can undergo electronic transitions as well as rotational and vibrational ones.
Generally, the energy difference between the ground and excited electronic level is such that the
radiation absorbed for the transition is in the ultraviolet/visible regions.
We represent the electronic states of a molecule as potential energy curves. Within the energy
wells, lines representing vibrational states are present. Within each vibrational state, lines
representing rotational states are present.
CHEM 4AL Section 102 (Monday 26pm)
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Vibronic transitions are the vibrational transitions in electronic spectra.
Here is a potential energy diagram of O
2
, showing the multiple electronic states and their
associated vibrational states. Note that R, along the xaxis, is a measure of the internuclear
distance.
How would you represent the transition from the ground to excited state visually?
Important guidelines for drawing any graphs:
Draw and label axes! Be sure to include units.
Label any key points on the graph.
For potential energy diagrams, we will add:
Explicitly label the ground and excited states!
CHEM 4AL Section 102 (Monday 26pm)
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Label the potential energy minima, i.e. the lowest part of the well.
Do not forget to include vibrational levels! (You do not need to draw rotational levels.)
General idea: If you can label it, label it.
Transition Metal Chemistry
Question: What is a transition metal complex?
Transition metal complexes contain a transition metal center, and molecules (called ligands)
bound to the metal center. Generally, they have the form [ML
n
]
x+
.
We say that ligands have a covalent type bond or a dative type bond.
What we need to know about ligands:
1. The charge of the ligand.
i.e. The Cl ligand has a charge of 1.
2. The number of electrons donated by the ligand in its bond to the metal.
Some of the more common ligands and their electron donating count are listed below.
CHEM 4AL Section 102 (Monday 26pm)
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Crystal Field Theory
Definition: Crystal field theory models the effect that introducing ligands to a metal center will
have on the energies of the metal dorbitals.
The orbitals which overlap the ligands will be split such that they are higher in energy,
whereas those which do not are split such that they are lower in energy.
Kinetic Theory of Gases
The ideal gas law states that pressure, volume, and temperature are related by the equation
PI = nRI
or
PI = Nk
B
I
where n is the moles of gas
N is the molecules of gas
In order to use the ideal gas law, we assume that the gas is composed of constantlymoving
particles which (a) are sufficiently far apart to avoid intermolecular interactions, and (b) occupy
zero volume.
Experimentally, most (sufficiently dilute) gases behave ideally at 1 atm and 0 °C to approximately
1%.
Some Things to Remember:
‐ The term k
B
T is a unit of energy. Note that each translational degree of freedom in a
particle contributes
1
2
k
B
I of energy to the particle.
‐ We derived the ideal gas law by considering the momentum change associated with a gas
of density η striking the wall of a container with a speed of v
x
in the xdirection within a
certain interval of time (Δt).
# molcculcs striking tbc woll =
1
2
p:
x
A∆t
‐ The mean free path of molecules of diameter d in a gas of density η can be calculated
using
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Hcon Frcc Potb =
1
√2 nJ
2
p
At higher temperatures and pressures, the ideal gas law is an increasingly inaccurate description
of the behavior of gas particles!
Van der Waals Equation of State
To account for intermolecular interactions and molecular size, we present an improved version
of the ideal gas law:
_P +o
n
2
I
2
_(I nb) = nRI
Note that a accounts for attractions between molecules, and b accounts for the volume taken
up by each particle.
Intermolecular Potentials
We can represent the interactions between the atoms in a molecule using a potential energy
curve.
CHEM 4AL Section 102 (Monday 26pm)
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The actual potential energy curves of molecules can be modeled using different equations. In class,
we covered the LennardJones potential, which models the energy curve using the equation
I(R) = 4e _[
o
R
¸
12
[
o
R
¸
6
_
where ε represents the depth of the well
σ represents the size of the molecules
The minimum of the LennardJones potential represents the preferred molecular diameter.
Introduction to Thermodynamics
Basic Principles
Thermodynamics is the study of the properties and relationships between the various properties
of systems in equilibria.
Two important concepts in thermodynamics are work and heat, which refer to how energy is
transferred between a system and its surroundings.
‐ Work (w) is defined as the transfer of energy resulting from an imbalance of forces
between a system and its surroundings.
w = _P JI
‐ Heat (q) is defined as the transfer of energy resulting from a difference in temperature
between a system and its surroundings.
q = C∆I
where C is the heat capacity
The internal energy U is related to heat and work by
∆u = q +w
The enthalpy of a system is expressed as
∆E = ∆u +∆(PI)
Note that any ideal gas obeys the following relation:
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c
p
= c
¡
+R
We use thermodynamics to describe macroscopic systems.
Microscopic systems can be described using variables (r, p) and Schrödinger’s equation.
Macroscopic systems can be described using variables (T, P, V, E, n, etc.).
Over time, if measuring macroscopic properties, we obtain some average value.
Macroscopic properties can be either intensive or extensive.
Intensive properties are determined by the intrinsic properties of the system and do not
change as the size of the system changes.
Extensive properties change with the size of the system.
We relate macroscopic properties to each other using equations of state.
Definition: A microstate describes an instantaneous configuration of the microscopic variables
of a system.
Laws of Thermodynamics
Thermodynamics is the study of the relationship between properties of the macroscopic systems
in equilibrium. We define fundamental principles (“laws”) of thermodynamics to describe the
energetics of changes between macroscopic, stationary states of the system.
Zeroth Law of Thermodynamics
Two systems in thermal equilibrium with a third system are also in thermal equilibrium with
each other.
To define thermal equilibrium, consider two objects at different temperatures. When the two
objects contact one another, a transfer of heat occurs from the object at a higher temperature to
the object at a lower temperature.
CHEM 4AL Section 102 (Monday 26pm)
GSI: Christine Chang (chang@berkeley.edu)
Office Hours: (Dead Week) Tuesday 4:30 – 5:30 pm and Thursday 3:00 – 4:00 pm
First Law of Thermodynamics
The First Law is essentially a statement of the conservation of energy in a thermodynamic
system.
The change in a system’s internal energy is equal to the heat supplied to the system minus
the work done by the system.
∆u = q +w
Second Law of Thermodynamics
The Second Law is a statement of the tendency of a thermodynamic system towards disorder.
The entropy of a system is a measure of the disorder.
For an irreversible process, the entropy of the system plus its surroundings must increase.
For a reversible process, the entropy of the system plus its surroundings is constant.
JS =
Jq
¡c¡
JI
Using the definition of entropy, we can define the Gibbs Free Energy:
0 = E IS
Third Law of Thermodynamics
The Third Law is a statement about the behavior of a thermodynamic system in the zero
temperature limit.
As T → 0 K, only the lowestenergy microstates of a system will be populated.
o For systems with multiple minimumenergy microstates, the entropy approaches
a constant value.
o For systems with only one minimumenergy microstate, the entropy approaches
zero.
CHEM 4AL Section 102 (Monday 26pm)
GSI: Christine Chang (chang@berkeley.edu)
Office Hours: (Dead Week) Tuesday 4:30 – 5:30 pm and Thursday 3:00 – 4:00 pm
Carnot Cycle
Thermodynamics can give insight into the conversion of heat into work. Heat engines withdraw
energy as heat from a highertemperature thermal reservoir, converts some of this energy to
work, and discharges the rest of the energy as heat to lowertemperature thermal reservoir.
The Carnot cycle is an example of a thermodynamic cycle, which is where a system goes through
a series of different states before returning to its initial state. In the Carnot cycle, we experience
the following steps:
1) Reversible isothermal expansion: The gas expands at the hot temperature, T
h
.
Because the process is isothermal, the temperature does not change during the
process.
The gas absorbs heat energy and entropy from the hightemperature reservoir to
expand.
2) Reversible adiabatic (or “isentropic”) expansion: The gas expands without the gain or
loss of heat.
Because the process is adiabatic, heat does not change during the process.
The gas expands, doing work on its surroundings. The associated loss of energy
causes the gas to cool to the cold temperature, T
c
.
The entropy remains constant.
3) Reversible isothermal compression: The surroundings compress the gas at the cold
temperature, T
c
.
The surroundings do work on the gas, causing the gas to lose heat energy and
entropy to the lowtemperature reservoir and compress.
4) Reversible adiabatic (or “isentropic”) compression: The surroundings compress the gas
without the gain or loss of heat.
The surroundings do work on the gas, which cause the internal energy to increase.
This gain in energy heats the gas to the hot temperature, T
h
.
CHEM 4AL Section 102 (Monday 26pm)
GSI: Christine Chang (chang@berkeley.edu)
Office Hours: (Dead Week) Tuesday 4:30 – 5:30 pm and Thursday 3:00 – 4:00 pm
The entropy remains constant.
The Carnot cycle can be illustrated thusly:
Image source: Barclay Physics Wiki
Gibbs Free Energy and Equilibrium
The mathematical definition of Gibbs free energy (G) was given earlier:
0 = E  IS
In a chemical reaction at a constant temperature, the change in G is given as
∆0 = ∆E  I∆S
ìntc¡nuI
This change in G can elucidate the nature of a chemical process:
ΔG
system
> 0 for a nonspontaneous process.
ΔG
system
= 0 for a reversible process.
ΔG
system
< 0 for a spontaneous process.
Gibbs free energy is a measure of the maximum amount of nonexpansion which can be removed
from a closed system.
CHEM 4AL Section 102 (Monday 26pm)
GSI: Christine Chang (chang@berkeley.edu)
Office Hours: (Dead Week) Tuesday 4:30 – 5:30 pm and Thursday 3:00 – 4:00 pm
Image source: Harding at UCLA
We can calculate the ΔG° of a particular chemical reaction by using the free energy of formation
and number of moles for the products and the reactants.
∆0
o
= n
p¡od
∆0
],p¡oducts
o
n
¡cuct
∆0
],¡cuctunts
o
The enthalpy of a reaction, ΔH°, can be calculated similarly.
Relation to Equilibrium Constant
In a reaction, the equilibrium constant K is defined as
K =
proJucts]
rcoctonts]
For instance, if a reaction proceeds from aA + bB → cC + dD, we have
K =
C]
c
Ð]
d
A]
u
B]
b
The equilibrium constant is related to the Gibbs free energy by
∆0 = RI lnK
Equilibrium
Le Châtelier’s Principle
When a change is introduced to a chemical system at equilibrium, the equilibrium will shift to
oppose the change.
CHEM 4AL Section 102 (Monday 26pm)
GSI: Christine Chang (chang@berkeley.edu)
Office Hours: (Dead Week) Tuesday 4:30 – 5:30 pm and Thursday 3:00 – 4:00 pm
In terms of concentrations,
K =
∏proJucts]
moI p¡oduct
∏rcoctonts]
moI ¡cuctunt
We can write the same equation in terms of partial pressures.
K
P
=
∏(P
p¡od
)
moI p¡od
∏(P
¡cuct
)
moI ¡cuct
To calculate ΔG°, ΔH°, or ΔS° of a particular chemical reaction, we can use the standard G/H/S of
formation and number of moles for the products and the reactants.
∆0
o
= n
p¡od
∆0
],p¡oducts
o
n
¡cuct
∆0
],¡cuctunts
o
∆E
o
= n
p¡od
∆E
],p¡oducts
o
n
¡cuct
∆E
],¡cuctunts
o
∆S
o
= n
p¡od
∆S
],p¡oducts
o
n
¡cuct
∆S
],¡cuctunts
o
For a multistep reaction, we need to calculate the ΔG°, ΔH°, or ΔS° of each individual step and
sum them at the end.
When dealing with systems at equilibrium, we have to consider that there are three important
“time points” in that reaction.
1) Initial Time: This is your system at t
0
, happily at its initial state. The conditions during
this point in time are the initial reaction conditions.
2) Change Time: This is when the system reacts to come to equilibrium. We will see a
change in the reaction conditions.
3) Equilibrium Time: This is what your system looks like after equilibrium has been
established.
Using these ideas, we can construct what are called ICE tables (initial, change, equilibrium) in
order to simplify the process for us. This process is illustrated below, in the following example.
CHEM 4AL Section 102 (Monday 26pm)
GSI: Christine Chang (chang@berkeley.edu)
Office Hours: (Dead Week) Tuesday 4:30 – 5:30 pm and Thursday 3:00 – 4:00 pm
Acids and Bases
We have already learned some important concepts about acids and bases. Some vocabulary to
keep in mind:
Acid + Base ⇄ Conjugate Acid + Conjugate Base
HA+ B

⇄ HB + A

Definitions
The first definition of an acid and base was made by Arrhenius, who said that acids produce
hydrogen ions in aqueous solution, and bases produce hydroxide ions. The Arrhenius definition is
limited to aqueous acids and bases.
In chemistry today, we mainly use two principal definitions of acids and bases.
By the BrønstedLowry definition of acids and bases:
Acids are proton (H
+
) donors.
Bases are proton (H
+
) acceptors.
i.e. NH
4
+
+ OH

⇄ NH
3
+ H
2
O
NH
4
+
is a Brønsted acid, and OH

is a Brønsted base.
By the Lewis definition of acids and bases:
Acids are electron (e

) acceptors.
Bases are electron (e

) donors.
i.e. BF
3
+ F

⇄ BF
4

BF
3
is a Lewis acid, and F

is a Lewis base.
The Acid Dissociation Constant (K
a
)
Consider a generalized reaction for an acid in water:
HA(aq) ⇄ H
+
(aq) + A

(aq)
CHEM 4AL Section 102 (Monday 26pm)
GSI: Christine Chang (chang@berkeley.edu)
Office Hours: (Dead Week) Tuesday 4:30 – 5:30 pm and Thursday 3:00 – 4:00 pm
The equilibrium constant for this expression is:
K
a
=
B
+
]A

]
BA]
We call K
a
the acid dissociation constant because it measures the rate at which the acid
dissociates.
Note that K
a
is often expressed in terms of pK
a
. The relation between K
a
and pK
a
is:
pK
u
= log K
u
Acids and Acid Strength
We will examine the general equation for an acid below. (Note: This equation produces K
a
as its
equilibrium constant. Why?)
HA(aq) + H
2
O(l) ⇄ H
3
O
+
(aq) + A

(aq)
To measure acid and base strength we commonly use pH and pOH, where:
pE = logE
+
]
p0E = log0E

]
Acids can come in either the strong variety or the weak variety. Strong acids are acids in which
the reaction equilibrium lies strongly to the right. In other words, they dissociate readily. Strong
acids yield weak conjugate bases! Some common examples of strong acids include sulfuric acid,
hydrochloric acid, and perchloric acid. Calculating the pH of a strong acid is relatively simple.
Weak acids are acids in which the reaction equilibrium lies far to the left. Thus, a weak acid does
not dissociate very much in aqueous solution. Weak acids yield strong conjugate bases! Some
common examples of weak acids include phosphoric acid, nitrous acid, and hypochlorous acid.
To calculate the pH of a weak acid, we need to use ICE tables.
Amphoteric Substances
Note that water is an amphoteric substance. In other words, water can act as both an acid and a
base!
CHEM 4AL Section 102 (Monday 26pm)
GSI: Christine Chang (chang@berkeley.edu)
Office Hours: (Dead Week) Tuesday 4:30 – 5:30 pm and Thursday 3:00 – 4:00 pm
The autoionization for water is as follows:
2H
2
O(l) ⇄ H
3
O
+
(aq) + OH

(aq)
The equilibrium constant for this reaction is
K
w
= B
3
0
+
]0B

] = B
+
]0B

]
Experimentally, [H
+
] and [OH

] are both equal to 1.0 × 10
7
M, which means that
K
w
= 1.0 × 10
14
We can write that for an equilibrium expression,
pK
u
+pK
b
= 14 = pK
w
or
pE +p0E = 14 = pK
w
Acid/Base Stability
Recall that an acid is stronger if its conjugate base is weaker. Thus, a more stable conjugate base
gives rise to a stronger acid!
Buffers
A buffer is a solution which resists a change in its pH when either OH

or H
+
is added.
May contain a weak acid and its salt (i.e. HF with NaF) or a weak base and its salt (i.e.
NH
3
and NH
4
Cl).
To calculate the pH of a buffered solution, we should use an ICE table.
Organic Acids
An organic acid is an acid with a carbon atom backbone. We often see organic acids containing
the carbonyl (C=O) functional group.
Organic acids are usually weak acids. Some examples of organic acids include acetic acid and
benzoic acid.
CHEM 4AL Section 102 (Monday 26pm)
GSI: Christine Chang (chang@berkeley.edu)
Office Hours: (Dead Week) Tuesday 4:30 – 5:30 pm and Thursday 3:00 – 4:00 pm
Note that in the examples of acetic acid and benzoic acid, though the acid contains several
hydrogens, only the hydrogen attached to the –OH group is acidic. The other hydrogens in
organic acids are not acidic and will not dissociate in an acid!
Extensive credit for these notes go to Zumdahl, Gray, and Oxtoby.
(Chemistry, Chemical Bonds: An Introduction to Atomic and Molecular Structure, and Principles of Modern Chemistry)