Chapter 05: Periodicity and Atomic Structure

Quantum Mechanics
Nature of the Atom and Bonding
Taken from a Combination of Books
To accompany Tro:
A Molecular Approach,
Chapters 7-10
CHM 112 University of Miami
The Periodic Table
The Periodic Table
was Developed in
1869.
It is the most
important organizing
principle in Chemistry
Chapter 05: Periodicity and Atomic Structure
Mendeleev
order elements by atomic mass - saw a repeating
pattern of properties
Periodic Law When the elements are arranged
in order of increasing atomic mass, certain sets
of properties recur periodically.
put elements with similar properties in the same
column
used pattern to predict the existence of
undiscovered elements and their properties.
(Mendeleev was the first to do this)
Mendeleev
H
2
O He(no) Li
2
O BeO B
2
O
3
CO
2
N
2
O
5
O
3
OF
2
Ne(no) Na
2
O MgO Al
2
O
3
SiO
2
P
2
O
5
SO
3
OCl
2
Ar (no)
2:1 - 2:1 1:1 1:1 1:2 2:5 - 1:2 - 2:1 1:1 2:3 1:2 2:5 1:3 1:2 -
Investigated the way elements reacted with oxygen
H
2
O He(no) Li
2
O BeO B
2
O
3
CO
2
N
2
O
5
O
3
OF
2
Ne(no) Na
2
O MgO Al
2
O
3
SiO
2
P
2
O
5
SO
3
OCl
2
Ar (no)
2:1 - 2:1 1:1 1:1 1:2 2:5 - 1:2 - 2:1 1:1 2:3 1:2 2:5 1:3 1:2 -
H
2
O He(no) Li
2
O BeO B
2
O
3
CO
2
N
2
O
5
O
3
OF
2
Ne(no) Na
2
O MgO Al
2
O
3
SiO
2
P
2
O
5
SO
3
OCl
2
Ar (no)
2:1 - 2:1 1:1 1:1 1:2 2:5 - 1:2 - 2:1 1:1 2:3 1:2 2:5 1:3 1:2 -
Chapter 05: Periodicity and Atomic Structure
H
2
O He(no) Li
2
O BeO B
2
O
3
CO
2
N
2
O
5
O
3
OF
2
Ne(no) Na
2
O Mg
O
Al
2
O
3
SiO
2
P
2
O
5
SO
3
OCl
2
Ar (no)
2:1 - 2:1 1:1 1:1 1:2 2:5 - 1:2 - 2:1 1:1 2:3 1:2 2:5 1:3 1:2 -
H
2
O He(no)
Li
2
O BeO B
2
O
3
CO
2
N
2
O
5
O
3
OF
2
Ne(no)
Na
2
O MgO Al
2
O
3
SiO
2
P
2
O
5
SO
3
OCl
2
Ar (no)
Atomic radius
As one travels across a
period in the periodic
table, the atom gets
smaller
As one travels down a
group in the periodic table,
the atoms get larger
Atomic Radius is a
Periodic Property
Chapter 05: Periodicity and Atomic Structure
Mendeleev's Predictions
Mendeleev was the first to propose that there were
elements that existed but had not yet been discovered.
He also predicted their properties with great accuracy.
The Periodic Table
At the same time as the periodic table was being
developed.
1865 Lincoln was assassinated
1865 End of Civil War
1868 Ulysses S. Grant was elected president
1868 Lockyer and Falkland discovered the element
helium in the sun.
1869 Suez Canal opened
1869 Mendeleev publishes his original periodic table.
Chapter 05: Periodicity and Atomic Structure
But why do such patterns exist?
Mendeleevs Periodic Law allows us to predict what the
properties of an element will be based on its position
on the table
it doesnt explain why the pattern exists
Quantum Mechanics is a theory that explains why the
periodic trends in the properties exist.
The validity of quantum mechanics in chemistry is
evident by its ability to predict the periodic table.
Lets try to understand a little quantum mechanics
Light and the Atom
Chapter 05: Periodicity and Atomic Structure
Light and the Atom
Light and the Atom
Chapter 05: Periodicity and Atomic Structure
Light and the Atom
Scientists observed that different elements would emit different
colors when ignited.
In fact helium was first discovered in the sun by looking at the
colors of the spectrum of the sun.
This must have something to do with the actual structure of the
atoms.
They believed that light or electromagnetic radiation served as a
window into the structure of the atom itself.
IN order to proceed we must learn more
about electromagnetic radiation.
Electromagnetic Radiation
Chapter 05: Periodicity and Atomic Structure
Electromagnetic Radiation
Frequency (v, Greek nu): Number of peaks that pass a
given point per unit time.
Wavelength (, Greek lambda): Distance from one wave
peak to the next.
Amplitude: Height measured from the center of the wave.
The square of the amplitude gives intensity.
Electromagnetic Radiation
Frequency (v, Greek
nu): Number of peaks
that pass a given point
per unit time.
Wavelength (, Greek
lambda): Distance from
one wave peak to the
next.
Amplitude: Height
measured from the
center of the wave. The
square of the amplitude
gives intensity.
Chapter 05: Periodicity and Atomic Structure
Electromagnetic Radiation
Electromagnetic Radiation
Speed of a wave is the wavelength (in meters) multiplied
by its frequency in reciprocal seconds.
Wavelength x Frequency = Speed of light
(m) x v (s
1
) = c (m/s)
Chapter 05: Periodicity and Atomic Structure
The red light in a laser pointer comes from a diode laser that has a lambda of
about( = ) 630 nm.
What is the frequency of the light?
c = 2.9979 x 10
8
m/s
Electromagnetic Radiation
What is the frequency of a gamma ray with = 3.56 X 10
-11
m?
What is the wavelength of an FM
radio wave with = 102.5 MHz?
Electromagnetic Radiation
Chapter 05: Periodicity and Atomic Structure
Electromagnetic Radiation
Chapter 05: Periodicity and Atomic Structure
Chapter 05: Periodicity and Atomic Structure
Spectra
when atoms or molecules absorb energy, that energy is
often released as light energy fireworks, neon lights,
etc.
when that light is passed through a prism, a pattern is
seen that is unique to that type of atom or molecule
the pattern is called an emission spectrum
Rydberg analyzed the spectrum of hydrogen and found
that it could be described with an equation that involved
an inverse square of integers
Chapter 05: Periodicity and Atomic Structure
Emission Spectra
Exciting Gas Atoms to Emit Light
with Electrical Energy
Hg He H
Chapter 05: Periodicity and Atomic Structure
Examples of Spectra
Oxygen spectrum
Neon spectrum
Identifying Elements with
Flame Tests
Na K Li Ba
Chapter 05: Periodicity and Atomic Structure
Emission vs. Absorption Spectra
Spectra of Mercury
Electromagnetic Radiation - Waves
As we have seen electromagnetic radiation is defined as
a wave.
Sometimes however these waves exhibit particle like
properties.
Black body radiation Max Planck
Photoelectric Effect Albert Einstein
Wave particle duality
Chapter 05: Periodicity and Atomic Structure
Radiation as particles
Max Planck (18581947): proposed the energy from
blackbody radiation only emitted in discrete packets
called quanta, not as a continuously variable waves.
The amount of energy depends on the frequency of
emitted light:
h is Plancks constant and
is a proportionality
between E and v
So from the frequency of the
wave, we can calculate its energy.
The Photoelectric Effect
it was observed that many metals emit electrons when a
light above a certain threshold frequency shines on
their surface (Photoelectric Effect)
according to this theory, if the wavelength of light is
made shorter, or the light waves intensity made
brighter, electrons should be ejected by the metal.
This did not happen. The intensity of the light did not
have any effect at below a threshold frequency.
Chapter 05: Periodicity and Atomic Structure
Atomic Spectra
Albert Einstein
(18791955):
Used the idea of
quanta to explain the
photoelectric
effect.
He proposed that
light behaves as a
stream of particles
called photons.
The Photoelectric Effect
Chapter 05: Periodicity and Atomic Structure
The Photoelectric Effect
The Problem
in experiments with the photoelectric effect, it was
observed that there was a maximum wavelength for
electrons to be emitted
called the threshold frequency
regardless of the intensity
it was also observed that high frequency light with a
dim source caused electron emission without any lag
time
Einsteins Explanation
Einstein proposed that the light energy was delivered to
the atoms in packets, called quanta or photons. He
borrowed the term from Planck.
The photoelectric effect
shows that light sometimes
acts as particles or packets
called quanta.
Chapter 05: Periodicity and Atomic Structure
Bohrs Model
Neils Bohr proposed that the electrons could only have
very specific amounts of energy fixed amounts =
quantized
the electrons traveled in orbits that were a fixed
distance from the nucleus stationary states
therefore the energy of the electron was proportional
the distance the orbital was from the nucleus
electrons emitted radiation when they jumped from an
orbit with higher energy down to an orbit with lower
energy
the distance between the orbits determined the
energy of the photon of light produced
Atomic Spectra
Atomic spectra: Result from excited atoms
emitting light.
Line spectra: Result from electron
transitions between specific energy levels.
Chapter 05: Periodicity and Atomic Structure
Electronic Transitions
Electronic Transitions
Electronic Transitions
Electronic Transitions
Chapter 05: Periodicity and Atomic Structure
Electronic Transitions
The positions of these lines may be predicted using a simple equation
Electronic Transitions
This equation is defined empirically. It just
happens to fit. It had no relation to any particular
model of the atom.
is the
wavelength of
the emitted
light.
n and m are quantum
numbers. They had no
particular meaning except
that they were integers.
Chapter 05: Periodicity and Atomic Structure
Bohr Model of H Atoms
Atomic Spectra- Bohr model
Line Spectra
Chapter 05: Periodicity and Atomic Structure
Quantum Mechanics
Niels Bohr (18851962): Described atom as electrons circling
around a nucleus and concluded that electrons have specific
energy levels. These energy levels are quantized. They are
indicated by one quantum number, n. n may be equal to 1, 2,
3..
It can never be any non integral number
When light is emitted the electrons are jumping from a higher
energy level to another. When light is absorbed electrons are
jumping from a lower energy orbital to a higher one
Atomic Spectra- Bohr model
Line Spectra
Bohr model electrons are in orbit
around the nucleus. Light is
emitted when electrons go from
a high energy to low energy.
From a low n to an even lower
value of n orbit .
Chapter 05: Periodicity and Atomic Structure
WaveParticle Duality
Louis de Broglie (18921987): Suggested waves can behave as
particles and particles can behave as waves. This is called wave
particle duality.
For Light :
=
h
mc
=
h
p
For a Particle :
=
h
mv
=
h
p
Quantum Mechanics
Erwin Schrdinger (18871961): Proposed quantum
mechanical model of atom, which focuses on wavelike
properties of electrons. He assumed that electrons
were waves and applied the principles of wave mechanics.
Prior to Schrodinger, electrons were treated as particles
which had some wavelike properties.
Chapter 05: Periodicity and Atomic Structure
Quantum Mechanics
Werner Heisenberg (19011976): Showed that it is
impossible to know (or measure) precisely both the
position and velocity (or the momentum) at the same
time.
The simple act of seeing an electron would change its
energy and therefore its position.
Quantum Mechanics
Erwin Schrdinger (18871961): Developed a compromise
which calculates both the energy of an electron and the
probability of finding an electron at any point in the
molecule.
This is accomplished by solving the Schrdinger equation,
resulting in the wave function, +.
Chapter 05: Periodicity and Atomic Structure
Quantum Numbers
Wave functions describe the behavior of electrons.
Each wave function contains three variables called
quantum numbers:
Principal Quantum Number (n)
Angular-Momentum Quantum Number (l)
Magnetic Quantum Number (m
l
)
The term quantum number
means that it is either
this number or this
number never in between.
Quantum Numbers
Principal Quantum Number (n): Defines the size and
energy level of the orbital. n = 1, 2, 3,
As n increases, the electrons get farther from the
nucleus.
As n increases, the electrons energy increases.
Each value of n is generally called a shell.
Chapter 05: Periodicity and Atomic Structure
Quantum Numbers
Angular-Momentum Quantum Number (l): Defines
the three-dimensional shape of the orbital.
For an orbital of principal quantum number n, the
value of l can have an integer value from 0 to n 1.
This gives the subshell notation:
l = 0 = s orbital l = 1 = p orbital
l = 2 = d orbital l = 3 = f orbital
l = 4 = g orbital
Quantum Numbers
Magnetic Quantum Number (m
l
): Defines the spatial
orientation of the orbital.
For orbital of angular-momentum quantum number, l, the
value of m
l
has integer values from l to +l.
This gives a spatial orientation of:
l = 0 giving m
l
= 0
l = 1 giving m
l
= 1, 0, +1
l = 2 giving m
l
= 2, 1, 0, 1, 2, and so on...
Chapter 05: Periodicity and Atomic Structure
Quantum Numbers
n=1
l=0
m
l
=0
Quantum Numbers
n=2
l=0,1
s and p
m
l
=0
and
ml = -
1,0,1
Chapter 05: Periodicity and Atomic Structure
Quantum Numbers
n=3
l=0,1,2
s , p , d
m
l
=0
and
ml = -1,0,1
and
ml =
-2,-1,0,1,2
Quantum Numbers
Spin Quantum Number:
The Pauli Exclusion
Principle states that no
two electrons can have
the same four quantum
numbers.
Chapter 05: Periodicity and Atomic Structure
Quantum Numbers
Quantum Numbers
Why cant an electron have the following quantum
numbers?
(a) n = 2, l = 2, m
l
= 1 (b) n = 3, l = 0, m
l
= 3
(c) n = 5, l = 2, m
l
= 1
Chapter 05: Periodicity and Atomic Structure
Quantum Numbers
Give orbital notations for electrons with the following
quantum numbers:
(a) n = 2, l = 1, m
l
= 1 (b) n = 4, l = 3, m
l
= 2
(c) n = 3, l = 2, m
l
= 1
Electron Radial Distribution
s Orbital Shapes:
Chapter 05: Periodicity and Atomic Structure
Electron Radial Distribution
p Orbital Shapes:
Electron Radial Distribution
d and f Orbital Shapes:
Chapter 05: Periodicity and Atomic Structure
Effective Nuclear Charge
Electron Configuration of Atoms
Pauli Exclusion Principle: No two electrons in an atom can
have the same quantum numbers (n, l, m
l
, m
s
).
Hunds Rule: When filling orbitals in the same subshell,
maximize the number of parallel spins.
Chapter 05: Periodicity and Atomic Structure
Electron Configuration of Atoms
Rules of Aufbau
Principle:
Lower n orbitals fill
first.
Each orbital holds
two electrons; each
with different m
s
.
Half-fill degenerate
orbitals before
pairing
electrons.
Electron Configuration of Atoms
Chapter 05: Periodicity and Atomic Structure
Electron Configuration of Atoms
Li |+ | 1s
2
2s
1
1s 2s
Be |+ |+ 1s
2
2s
2
1s 2s
B |+ |+ | 1s
2
2s
2
2p
1
1s 2s 2p
x
2p
y
2p
z
C |+ |+ | | 1s
2
2s
2
2p
2
1s 2s 2p
x
2p
y
2p
z
Electron Configuration of Atoms
N |+ |+ | | | 1s
2
2s
2
2p
3
1s 2s 2p
x
2p
y
2p
z
O |+ |+ |+ | | 1s
2
2s
2
2p
4
1s 2s 2p
x
2p
y
2p
z
Ne |+ |+ |+ |+ |+ 1s
2
2s
2
2p
5
1s 2s 2p
x
2p
y
2p
z
S [Ne] |+ |+ | | [Ne] 3s
2
3p
4
3s 3p
x
3p
y
3p
z
Chapter 05: Periodicity and Atomic Structure
Electron Configuration of Atoms
Give the ground-state electron configurations for:
Ne (Z = 10) Mn (Z = 25) Zn (Z = 30)
Eu (Z = 63) W (Z = 74) Lw (Z = 103)
Identify elements with ground-state configurations:
1s
2
2s
2
2p
4
1s
2
2s
2
2p
6
3s
2
3p
6
3d
10
4s
2
4p
6
5s
2
4d
6
1s
2
2s
2
2p
6
[Ar] 4s
2
3d
1
[Xe] 6s
2
4f
14
5d
10
6p
5
Electron Configuration of Atoms
Chapter 05: Periodicity and Atomic Structure
Electron Configuration of Atoms
Electron Configuration of Atoms
Anomalous Electron Configurations: Result from unusual
stability of half-filled & full-filled subshells.
Chromium should be [Ar] 4s
2
3d
4
, but is [Ar] 4s
1
3d
5
Copper should be [Ar] 4s
2
3d
9
, but is [Ar] 4s
1
3d
10
In the second transition series this is even more
pronounced, with Nb, Mo, Ru, Rh, Pd, and Ag having
anomalous configurations (Figure 5.20).
Chapter 05: Periodicity and Atomic Structure
Effective Nuclear Charge
Electron shielding
leads to energy
differences among
orbitals within a
shell.
Net nuclear charge
felt by an electron
is called the
effective nuclear
charge (Z
eff
).
Effective Nuclear Charge
Z
eff
is lower than actual
nuclear charge.
Z
eff
increases
toward nucleus
ns > np > nd > nf
This explains certain periodic
changes observed.
Chapter 05: Periodicity and Atomic Structure
Periodic Properties
Atomic
radius
Periodic Properties
Chapter 05: Periodicity and Atomic Structure
Multi electron atom
Energy levels for the
Hydrogen atom
(only one electron
present)
Energy levels for the
multi electron atom
(lower l value lower
energy)
Electron Configuration of Atom
Rules of Aufbau
Principle:
Lower n orbitals fill
first.
Each orbital holds
two electrons; each
with different m
s
.
Half-fill degenerate
orbitals before
pairing
electrons.
Chapter 05: Periodicity and Atomic Structure
Order of Subshell Filling
in Ground State Electron
Configurations
1s
2s 2p
3s 3p 3d
4s 4p 4d 4f
5s 5p 5d 5f
6s 6p 6d
7s
start by drawing a diagram
putting each energy shell on
a row and listing the subshells,
(s, p, d, f), for that shell in
order of energy, (left-to-right) next, draw arrows through
the diagonals, looping back
to the next diagonal
each time
Electron Configuration of Atoms
Pauli Exclusion Principle: No two electrons in an
atom can have the same quantum numbers (n, l,
m
l
, m
s
).
Hunds Rule: When filling orbitals in the same
subshell, maximize the number of parallel spins.
Chapter 05: Periodicity and Atomic Structure
Quantum Numbers
Why cant an electron have the following quantum
numbers?
(a) n = 2, l = 2, m
l
= 1 (b) n = 3, l = 0, m
l
= 3
(c) n = 5, l = 2, m
l
= 1
Quantum Numbers
Give orbital notations for electrons with the following
quantum numbers:
(a) n = 2, l = 1, m
l
= 1 (b) n = 4, l = 3, m
l
= 2
(c) n = 3, l = 2, m
l
= 1
Chapter 05: Periodicity and Atomic Structure
Electron Configuration of Atoms
Li |+ | 1s
2
2s
1
1s 2s
Be |+ |+ 1s
2
2s
2
1s 2s
B |+ |+ | 1s
2
2s
2
2p
1
1s 2s 2p
x
2p
y
2p
z
C |+ |+ | | 1s
2
2s
2
2p
2
1s 2s 2p
x
2p
y
2p
z
Electron Configuration of Atom
N |+ |+ | | | 1s
2
2s
2
2p
3
1s 2s 2p
x
2p
y
2p
z
O |+ |+ |+ | | 1s
2
2s
2
2p
4
1s 2s 2p
x
2p
y
2p
z
Ne |+ |+ |+ |+ |+ 1s
2
2s
2
2p
5
1s 2s 2p
x
2p
y
2p
z
S [Ne] |+ |+ | | [Ne] 3s
2
3p
4
3s 3p
x
3p
y
3p
z
Chapter 05: Periodicity and Atomic Structure
Electron Configuration of Atoms
Give the ground-state electron configurations for:
Ne (Z = 10) Mn (Z = 25) Zn (Z = 30)
Eu (Z = 63) W (Z = 74) Lw (Z = 103)
Identify elements with ground-state
configurations:
1s
2
2s
2
2p
4
1s
2
2s
2
2p
6
3s
2
3p
6
3d
10
4s
2
4p
6
5s
2
4d
6
1s
2
2s
2
2p
6
[Ar] 4s
2
3d
1
[Xe] 6s
2
4f
14
5d
10
6p
5
Electron Configuration of
Atoms
Chapter 05: Periodicity and Atomic Structure
Electron Configuration of Atoms
Anomalous Electron Configurations: Result from
unusual stability of half-filled & full-filled
subshells.
Chromium should be [Ar] 4s
2
3d
4
, but is [Ar] 4s
1
3d
5
Copper should be [Ar] 4s
2
3d
9
, but is [Ar] 4s
1
3d
10
In the second transition series this is even more
pronounced, with Nb, Mo, Ru, Rh, Pd, and Ag having
anomalous configurations
Electron Configuration of Atoms
Chapter 05: Periodicity and Atomic Structure
Two considerations are important in determining
the periodic properties of different elements.
Effective Nuclear Charge
Stability of electronic configuration as a neutral atom
Stability of electron configuration as an ion
Periodic Properties
94
Screening & Effective Nuclear
Charge
Chapter 05: Periodicity and Atomic Structure
Periodic Properties
Chapter 05: Periodicity and Atomic Structure
Ions and Ionic Radii
There is great stability associated with the noble gas
configurations. Main group elements either lose or
gain electrons to get to as close as possible to the
noble gas configuration.
When forming ions main group metals lose electrons and
become isoelectronic with the nearest noble gas.
Main group nonmetals gain electrons and become
isoelectronic with the nearest noble gas.
Ions and Ionic Radii
Main-group metals donate electrons from the
atoms highest-energy occupied atomic orbital.
Na: 1s
2
2s
2
2p
6
3s
1
= [Ne] 3s
1
Na
+
: 1s
2
2s
2
2p
6
= [Ne]
Mg: 1s
2
2s
2
2p
6
3s
2
= [Ne] 3s
2
Mg
2+
: 1s
2
2s
2
2p
6
= [Ne]
Al: 1s
2
2s
2
2p
6
3s
2
3p
1
= [Ne] 3s
2
3p
1
Al
3+
1s
2
2s
2
2p
6
= [Ne]
The highest energy occupies orbital is the orbital with the highest n value. If
both have the same n value then take from the highest l value.
Chapter 05: Periodicity and Atomic Structure
Ions and Ionic Radii
Main-group nonmetals accept electrons into
their lowest-energy unoccupied atomic orbital.
N: 1s
2
2s
2
2p
3
= [He] 2s
2
2p
3
= [Ne]
N
3
: 1s
2
2s
2
2p
6
= [He] 2s
2
2p
6
= [Ne]
O: 1s
2
2s
2
2p
4
= [He] 2s
2
2p
4
= [Ne]
O
2
: 1s
2
2s
2
2p
6
= [He] 2s
2
2p
6
= [Ne]
F: 1s
2
2s
2
2p
5
= [He] 2s
2
2p
5
= [Ne]
F

: 1s
2
2s
2
2p
6
= [He] 2s
2
2p
6
= [Ne]
Ions and Ionic Radii
Transition metals lose their valence-shell s-
electrons before losing their d-electrons.
Electrons with the highest n-quantum number
are lost first.
Fe: 1s
2
2s
2
3s
2
3p
6
4s
2
3d
6
= [Ar] 3d
6
4s
2
Fe
2+
: 1s
2
2s
2
3s
2
3p
6
3d
6
= [Ar] 3d
6
Fe
3+
: 1s
2
2s
2
3s
2
3p
6
3d
5
= [Ar] 3d
5
Note: it is best to write the
configuration in order of
increasing n value. Highest n
should be written furthest to
the right.
Chapter 05: Periodicity and Atomic Structure
Ions and Ionic Radii
Ions and Ionic Radii
Cations are smaller than their parent atom.
(Outer shell has been essentially removed.)
Anions are larger than their parent atom.
(Outer shell is more effectively shielded.
There are more electrons than protons.)
Chapter 05: Periodicity and Atomic Structure
More periodic properties
Ionization Energy E
I
Energy required to remove an electron
from a neutral atom in the gas state.
M + E
I
M
+
+1e
-
E
I
is always a positive number but in many cases it is much
smaller than in others.
We can predict the magnitude of E
I
by the position in the
periodic table.
E
I
is a function of the Effective nuclear charge and the
electron configurations of the atom and ion.
It has units of kJ/mol.
Ionization Energy
Chapter 05: Periodicity and Atomic Structure
Ionization Energy
Ionization Energy Trends:
Vary periodically. They trends are explained by changes
in Zeff, atomic radius and preferred electron
configurations
There are electron configurations which are more stable.
1. filled shell (noble gas configuration)
2. filled subshell
3. filled subshell
Ionization Energy
Ionization Energy Trend:
Ionization energies
vary periodically;
this is explained by
the changes in Z
eff
and the preferred electron
configurations.
Chapter 05: Periodicity and Atomic Structure
Ionization Energy
Ionization Energy Trend:
Ionization energies
vary periodically;
this is explained by
the changes in Z
eff
and the
preferred electron
configurations.
There are three types of
preferred electronic
configurations. These are
filled shell np
6
filled subshell ns
2
or np
6
or
nd
10
or nf
14
half filled subshell
np
3
or nd
5
or nf
7
Ionization Energy
As go across a row Ionization Energies increase with
increasing effective nuclear charge. The larger the Zeff, the
harder it is to remove an electron.
As go down a group the ionization energy decreases with
increasing atomic radius. The large the atom, the further
away the valence electron. The easier it is to remove the
electron.
Zeff
Chapter 05: Periodicity and Atomic Structure
Effective Nuclear charge
Li Be B C N O F Ne
Zeff
One would
expect that the
ionization energy
would increase
smoothly as it
goes across the
period
Ionization Energy 04
Chapter 05: Periodicity and Atomic Structure
Ionization Energy 04
Ionization Energy 04
Notice that
there are
exceptions to
the trend
Be is higher
than expected
while B is
lower
The same
thing happens
when we go
from Mg to Al
Again when go
from N to O there
is an unexpected
shift
Again with P
and S but not as
pronounced
These findings can be
explained by using the relative
stability of the electron
configuration.
Chapter 05: Periodicity and Atomic Structure
Preferred configurations
Lets look at the first ionization energies as a function
of electron configurations in going from Na to Ne
Li 1s
2
2s
1
1s
2
Be 1s
2
2s
2
1s
2
2s
1
B 1s
2
2s
2
2p
1
1s
2
2s
2
C 1s
2
2s
2
2p
2
1s
2
2s
2
2p
1
N 1s
2
2s
2
2p
3
1s
2
2s
2
2p
2
O 1s
2
2s
2
2p
4
1s
2
2s
2
2p
3
F 1s
2
2s
2
2p
5
1s
2
2s
2
2p
4
Ne 1s
2
2s
2
2p
6
1s
2
2s
2
2p
5
Preferred configurations
Lets look at the first ionization energies as a
function of electron configurations in going
from Na to Ne
Li 1s
2
2s
1
1s
2
Be 1s
2
2s
2
1s
2
2s
1
B 1s
2
2s
2
2p
1
1s
2
2s
2
C 1s
2
2s
2
2p
2
1s
2
2s
2
2p
1
N 1s
2
2s
2
2p
3
1s
2
2s
2
2p
2
O 1s
2
2s
2
2p
4
1s
2
2s
2
2p
3
F 1s
2
2s
2
2p
5
1s
2
2s
2
2p
4
Ne 1s
2
2s
2
2p
6
1s
2
2s
2
2p
5
The configuration
marked in red is
favored. If the favored
configuration is a
product, IE is lower
than expected. If
reactant is favored then
IE is larger than
expected
Chapter 05: Periodicity and Atomic Structure
Preferred configurations
Lets look at the first ionization energies as a
function of electron configurations in going
from Na to Ne
Li 1s
2
2s
1
1s
2
Be 1s
2
2s
2
1s
2
2s
1
B 1s
2
2s
2
2p
1
1s
2
2s
2
C 1s
2
2s
2
2p
2
1s
2
2s
2
2p
1
N 1s
2
2s
2
2p
3
1s
2
2s
2
2p
2
O 1s
2
2s
2
2p
4
1s
2
2s
2
2p
3
F 1s
2
2s
2
2p
5
1s
2
2s
2
2p
4
Ne 1s
2
2s
2
2p
6
1s
2
2s
2
2p
5
Be has a higher E
IE
than
B because B attains a
filled subshell and Be
has to take away an
electron from a filled
subshell.
Preferred configurations
Li 1s
2
2s
1
1s
2
Be 1s
2
2s
2
1s
2
2s
1
B 1s
2
2s
2
2p
1
1s
2
2s
2
C 1s
2
2s
2
2p
2
1s
2
2s
2
2p
1
N 1s
2
2s
2
2p
3
1s
2
2s
2
2p
2
O 1s
2
2s
2
2p
4
1s
2
2s
2
2p
3
F 1s
2
2s
2
2p
5
1s
2
2s
2
2p
4
Ne 1s
2
2s
2
2p
6
1s
2
2s
2
2p
5
Be has a higher E
IE
than B
because B attains a filled
subshell by removing and Be
has to take away an electron
from a filled subshell (the s
subshell).
Chapter 05: Periodicity and Atomic Structure
Ionization Energy 04
Preferred configurations
Li 1s
2
2s
1
1s
2
Be 1s
2
2s
2
1s
2
2s
1
B 1s
2
2s
2
2p
1
1s
2
2s
2
C 1s
2
2s
2
2p
2
1s
2
2s
2
2p
1
N 1s
2
2s
2
2p
3
1s
2
2s
2
2p
2
O 1s
2
2s
2
2p
4
1s
2
2s
2
2p
3
F 1s
2
2s
2
2p
5
1s
2
2s
2
2p
4
Ne 1s
2
2s
2
2p
6
1s
2
2s
2
2p
5
The same thing can
be said for N and O.
O attains a more
stable configuration
(half filled subshell)
and loses a more
stable configuration
(half-filled subshell)
Chapter 05: Periodicity and Atomic Structure
Ionization Energy 04
In summary ionization energy trends follow Zeff. There are
small anomalies due to preferred electron configurations.
Ionization Energy
Arrange the elements Se, Cl and S in order of increasing
ionization energy.
Chapter 05: Periodicity and Atomic Structure
Ionization Energy
Arrange the elements Ga, Ge As Se in order of
increasing ionization energy.
Electron Affinity
Energy change that occurs when an
electron is added to an isolated atom in
the gaseous state.
Abbreviation is E
ea
, it has units of
kJ/mol.
Chapter 05: Periodicity and Atomic Structure
Electron Affinity 01
Energy change that occurs when an
electron is added to an isolated atom in
the gaseous state.
Abbreviation is E
ea
, it has units of
kJ/mol.
Electron Affinity 02
Electron Affinity Trend:
the stability of the electron configuration.
Electron-electron repulsion
Everything else is not really as important. Zeff
also effects the E
EA
but not nearly as much as in
E
IE
.
Chapter 05: Periodicity and Atomic Structure
Electron Affinity
Li 1s
2
2s
1
1s
2
2s
2
Be 1s
2
2s
2
1s
2
2s
2
2p
1
B 1s
2
2s
2
2p
1
1s
2
2s
2
2p
2
C 1s
2
2s
2
2p
2
1s
2
2s
2
2p
3
N 1s
2
2s
2
2p
3
1s
2
2s
2
2p
4
O 1s
2
2s
2
2p
4
1s
2
2s
2
2p
5
F 1s
2
2s
2
2p
5
1s
2
2s
2
2p
6
Ne 1s
2
2s
2
2p
6
1s
2
2s
2
2p
6
3s
1
Again the favored
configurations are
in red.
The easiest to add an
electron to are the
ones where the
products are favored
configuration.
Noble gas configuration
is more important than
filled subshell than half
filled subshell.
Electron Affinity
Li 1s
2
2s
1
1s
2
2s
2
Be 1s
2
2s
2
1s
2
2s
2
2p
1
B 1s
2
2s
2
2p
1
1s
2
2s
2
2p
2
C 1s
2
2s
2
2p
2
1s
2
2s
2
2p
3
N 1s
2
2s
2
2p
3
1s
2
2s
2
2p
4
O 1s
2
2s
2
2p
4
1s
2
2s
2
2p
5
F 1s
2
2s
2
2p
5
1s
2
2s
2
2p
6
Ne 1s
2
2s
2
2p
6
1s
2
2s
2
2p
6
3s
1
The most negative electron
affinity (easiest to do) is F
since a noble gas
configuration would result.
The next most negative
would be Carbon
After that it would be Li
Chapter 05: Periodicity and Atomic Structure
Electron Affinity
Electron Affinity
Arrange the elements Na, Cl, Si, Al in order of
increasing (more negative E
EA
). Explain reasoning
Chapter 05: Periodicity and Atomic Structure
Ionic Bonds and Ionic Solids
Ionic bonds:
Form when an
element with a small
E
i
value comes in
contact with an
element with a
negative E
ea
value.
Examples of this would be any Group
IA metal atom (low E
I
) with any
Group VIIA (negative E
EA
)
Ionic Bonds and Ionic Solids 02
Sodium Chloride (NaCl): Sodium Chloride (NaCl):
The reason for
ionic bond
formation is the
attainment of a
noble gas
configuration of
electrons.
Since for Na E
IE
is
low and for Cl E
EA
is very negative, Cl
will take an electron
from Na and both
will have the s
2
p
6
Chapter 05: Periodicity and Atomic Structure
Ionic Bonds
The electrostatic attraction of the cation (positively
charged ion) for the anion (negatively charged ion) is
the reason these ions stay together in what is known
as a lattice.
If the atoms have a higher E
IE
and a more negative E
EA
then the
atoms will not give up or accept the electrons as easily. Instead
these atoms end up sharing electrons and this is called covalent
bonding.
132
Types of Bonding
metal cation
non metal
anion
non metal + non
metal shared
electrons
metal + metal
sea of loose
electrons
Chapter 05: Periodicity and Atomic Structure
Ionic Bonding
Bonding between a metal and a nonmetal
Metals (low ionization energy)
lose electrons
become cation
Nonmetals (high electron affinity)
gain electrons
become anion
133
134
Ionic Bonds
electrons from the metal atoms are transferred to the
nonmetal atoms
metals have low ionization energy, relatively easy to
remove an electron from
nonmetals have high electron affinities, relatively
good to add electrons to
Chapter 05: Periodicity and Atomic Structure
135
Determining the Number of Valence Electrons
in an Atom
the column number on the Periodic Table will tell
you how many valence electrons a main group
atom has
1A 2A 3A 4A 5A 6A 7A 8A
Li Be B C N O F Ne
1 e
-1
2 e
-1
3 e
-1
4 e
-1
5 e
-1
6 e
-1
7 e
-1
8 e
-1
136
Lewis Symbols of Atoms
aka electron dot symbols
use symbol of element to represent nucleus
and inner electrons
use dots around the symbol to represent
valence electrons
Chapter 05: Periodicity and Atomic Structure
137
Lewis Symbols of Ions
Cations have Lewis symbols without valence electrons
Lost in the cation formation
Anions have Lewis symbols with 8 valence electrons
Electrons gained in the formation of the anion
Li Li
+1
139
Lewis Theory and Ionic Bonding
Lewis symbols can be used to represent the transfer of
electrons from metal atom to nonmetal atom, resulting
in ions that are attracted to each other and therefore
bond
+ Li
+
Chapter 05: Periodicity and Atomic Structure
Tro, Chemistry: A
Molecular Approach
140
Predicting Ionic Formulas
Using Lewis Symbols
electrons are transferred until the metal loses
all its valence electrons and the nonmetal has an
octet
numbers of atoms are adjusted so the electron
transfer comes out even
2 Li
+
Li
2
O
141
Properties of Ionic Compounds
Melting an Ionic Solid
Does not conduct
electricity ions do
not move
Conduct electricity
ions free to move
molten salt
Chapter 05: Periodicity and Atomic Structure
142
Conductivity of NaCl
in NaCl(s), the ions
are stuck in position
and not allowed to
move to the charged
rods
in NaCl(aq), the
ions are separated
and allowed to
move to the charged
rods
143
Energetics of Ionic Bond Formation
the ionization energy of the metal is endothermic
Na(s) Na
+
(g) + 1 e

AH = +603 kJ/mol
the electron affinity of the nonmetal is
exothermic
Cl
2
(g) + 1 e

Cl

(g) AH = 227 kJ/mol

generally, the ionization energy of the metal is
larger than the electron affinity of the
nonmetal, therefore the formation of the ionic
compound should be endothermic
but the heat of formation of most ionic
compounds is exothermic and generally large;
Why?
Na(s) + Cl
2
(g) NaCl(s) AH
f
= -410 kJ/mol
Chapter 05: Periodicity and Atomic Structure
144
Energetics of Ionic Bond Formation
Gives us an opportunity to use Hesss Law
Enthalpy is a state function. In a reaction, the
same enthalpy change will result regardless on
the path from Reactants to products.
Enthalpy of Formation of NaCl(s) can be measured
experimentally
Na(s) + Cl
2
(g) NaCl(s) AH
f
= -410 kJ/mol
Lets carry out this reaction in steps.
145
Na(s) + Cl
2
(g) NaCl(s) H
f
= -410 kJ
Na(g)
Cl(g)
Na
+
(g)
Cl
-1
(g)
+
H
4
H
1 H
1
= H
vap
H
2
H
2
= IE
H
4
= -EA
H
3
H
3
= BDE
H
5
H
5
= H
lattice energy
H
f
= H
vap
+ IE + BDE EA+ H
lattice energy
H
lattice energy
= H
f
- (H
vap
+ IE + BDE EA)
H
f
=H
1
+H
2
+H
3
+H
4
+H
5
Chapter 05: Periodicity and Atomic Structure
146
147
Practice - Given the Information
Below, Determine the Lattice Energy
of MgCl
2
Mg(s) Mg(g) AH
1

f
= +147.1 kJ/mol
Cl
2
(g) Cl(g) AH
2

f
= +121.3 kJ/mol
Mg(g) Mg
+1
(g) AH
3

f
= +738
kJ/mol
Mg
+1
(g) Mg
+2
(g) AH
4

f
= +1450 kJ/mol
Cl(g) Cl
-1
(g) AH
5

f
= -349 kJ/mol
Mg(s) + Cl
2
(g) MgCl
2
(s) AH
6

f
= -641.3 kJ/mol
Chapter 05: Periodicity and Atomic Structure
148
Practice - Given the Information
Below, Determine the Lattice Energy
of MgCl
2
Mg(s) Mg(g) AH
1

f
= +147.1 kJ/mol
Cl
2
(g) Cl(g) AH
2

f
= +121.3 kJ/mol
Mg(g) Mg
+1
(g) AH
3

f
= +738 kJ/mol
Mg
+1
(g) Mg
+2
(g) AH
4

f
= +1450 kJ/mol
Cl(g) Cl
-1
(g) AH
5

f
= -349 kJ/mol
Mg(s) + Cl
2
(g) MgCl
2
(s) AH
6

f
= -641.3
kJ/mol
149
Lattice Energy
the lattice energy is the energy released when
the solid crystal forms from separate ions in
the gas state
always exothermic
can be calculated (Born Haber Cycle)
lattice energy depends directly on size of
charges and inversely on distance between ions
Chapter 05: Periodicity and Atomic Structure
150
Trends in Lattice Energy
Ion Size
the force of attraction between charged particles is
inversely proportional to the distance between them
larger ions mean the center of positive charge (nucleus
of the cation) is farther away from negative charge
(electrons of the anion)
larger ion = weaker attraction = smaller lattice
energy
151
Lattice Energy vs.
Ion Size
Metal Chloride
Lattice Energy
(kJ/mol)
LiCl -834
NaCl -787
KCl -701
CsCl -657
Chapter 05: Periodicity and Atomic Structure
152
Trends in Lattice Energy
Ion Charge
the force of attraction between
oppositely charged particles is
directly proportional to the
product of the charges
larger charge means the ions are
more strongly attracted
larger charge = stronger
attraction = larger lattice energy
of the two factors, ion charge
generally more important
Lattice Energy =
-910 kJ/mol
Lattice Energy =
-3414 kJ/mol
153
Example 9.2 Order the following ionic
compounds in order of increasing
magnitude of lattice energy.
CaO, KBr, KCl, SrO
First examine the ion charges and
order by product of the charges
Ca
2+
& O
2-
, K
+
& Br

,
K
+
& Cl

, Sr
2+
& O
2
(KBr, KCl) < (CaO, SrO)
Then examine the ion sizes of
each group and order by radius;
larger < smaller
(KBr, KCl) same cation,
Br

> Cl

(same Group)
KBr < KCl < (CaO, SrO)
(CaO, SrO) same anion,
Sr
2+
> Ca
2+
(same Group)
KBr < KCl < SrO < CaO
Chapter 05: Periodicity and Atomic Structure
155
Covalent Bonding
Predictions from Lewis Theory
Lewis theory allows us to predict the formulas of
molecules
Lewis theory predicts that some combinations
should be stable, while others should not
Lewis theory predicts in covalent bonding that the
attractions between atoms are directional
Tro, Chemistry: A
Molecular Approach
156
Covalent Bonding
Model vs. Reality
molecular compounds have low melting points and
boiling points
MP generally < 300C
molecular compounds are found in all 3 states at room
temperature
melting and boiling involve breaking the
attractions between the molecules, but not the
bonds between the atoms
the covalent bonds are strong
the attractions between the molecules are generally
weak
the polarity of the covalent bonds influences the
strength of the intermolecular attractions
Chapter 05: Periodicity and Atomic Structure
Tro, Chemistry: A
Molecular Approach
157
Intermolecular Attractions vs.
Bonding
158
Covalent Bonding
Model vs. Reality
some molecular solids are brittle and hard, but many are
soft and waxy
the kind and strength of the intermolecular
attractions varies based on many factors
the covalent bonds are not broken, however, the
polarity of the bonds has influence on these
attractive forces
Chapter 05: Periodicity and Atomic Structure
159
Covalent Bonding
Model vs. Reality
molecular compounds do not conduct electricity in
the liquid state
in molecular solids, there are no charged particles
around to allow the material to conduct
molecular acids conduct electricity when
dissolved in water, but not in the solid state
when dissolved in water, molecular acids are ionized,
and have the ability to move through the structure
and therefore conduct electricity
160
Electronegativity
Tendency of an element to attract electrons when bonded
Atoms with greater electronegativity will
pull the electrons in the bond closer to its side
have a larger electron density than the other
the result is a polar covalent bond
the end with the larger electron density gets a partial
negative charge
the end that is electron deficient gets a partial positive
charge
Chapter 05: Periodicity and Atomic Structure
161
Electronegativity Scale
162
HF
H F

o+ o
EN 2.1 EN 4.0
Chapter 05: Periodicity and Atomic Structure
163
Electronegativity Scale
164
Electronegativity
increases across period (left to right) and
decreases down group (top to bottom)
fluorine is the most electronegative element
francium is the least electronegative element
the larger the difference in electronegativity, the
more polar the bond
negative end toward more electronegative atom
Chapter 05: Periodicity and Atomic Structure
165
Electronegativity and Bond Polarity
If difference in electronegativity between bonded
atoms is 0, the bond is pure covalent
If difference in electronegativity between bonded
atoms is 0.1 to 0.4, the bond is nonpolar covalent
If difference in electronegativity between bonded
atoms 0.5 to 1.9, the bond is polar covalent
If difference in electronegativity between bonded
atoms larger than or equal to 2.0, the bond is
ionic
166
Bond Polarity
EN
Cl
= 3.0
3.0 - 3.0 = 0
Pure Covalent
EN
Cl
= 3.0
EN
H
= 2.1
3.0 2.1 = 0.9
Polar Covalent
EN
Cl
= 3.0
EN
Na
= 1.0
3.0 0.9 = 2.1
Ionic
Chapter 05: Periodicity and Atomic Structure
Tro, Chemistry: A
Molecular Approach
167
Water a Polar Molecule
stream of
water
attracted
to a
charged
glass rod
stream of
hexane
not
attracted
to a
charged
glass rod
168
Example 9.3(c) - Determine whether
an N-O bond is ionic, covalent, or
polar covalent.
Determine the electronegativity of each
element
N = 3.0; O = 3.5
Subtract the electronegativities, large minus
small
(3.5) - (3.0) = 0.5
If the difference is 2.0 or larger, then the
bond is ionic; otherwise its covalent
difference (0.5) is less than 2.0, therefore
covalent
If the difference is 0.5 to 1.9, then the bond
is polar covalent; otherwise its covalent
difference (0.5) is 0.5 to 1.9, therefore polar
covalent
Chapter 05: Periodicity and Atomic Structure
169
Lewis Structures
of Molecules
shows pattern of valence electron distribution in the
molecule
useful for understanding the bonding in many compounds
allows us to predict shapes of molecules
allows us to predict properties of molecules and how
they will interact together
170
Lewis Structures
use common bonding patterns
C = 4 bonds & 0 lone pairs, N = 3 bonds & 1 lone
pair, O= 2 bonds & 2 lone pairs, H and halogen = 1
bond, Be = 2 bonds & 0 lone pairs, B = 3 bonds &
0 lone pairs
often Lewis structures with line bonds have the
lone pairs left off
their presence is assumed from common bonding
patterns
structures which result in bonding patterns
different from common have formal charges
B C
N O F
Chapter 05: Periodicity and Atomic Structure
171
Lewis Structures
S = N A
N - number of electrons if each atom had the
Noble gas configuration ( 8 for all elements
except H)
A- is the number available electrons(sum of the
valence electrons for each atom in molecule)
S number of shared electrons in molecule.
Writing Lewis Structures of
Molecules HNO
3
1) Write skeletal structure
H always terminal
in oxyacid, H outside attached to Os
make least electronegative atom
central
N is central
2) Count valence electrons
sum the valence electrons for
each atom
add 1 electron for each
charge
subtract 1 electron for each +
charge
total is A (number of available
A (valence
electrons
N = 5
H = 1
O
3
= 36 = 18
Chapter 05: Periodicity and Atomic Structure
173
Writing Lewis Structures of
Molecules HNO
3
3) Calculate N, the number of electrons if all
atoms had noble gas configuration (8 for
all atoms except H)
N
4 X 8 = 32
1 x 2 = 2
N = 34
A (valence
electrons
N = 5
H = 1
O
3
= 36 = 18
A= 24 e
-
HNO
3
must have 5
bonds and 7 lone pairs
174
Possible Lewis structures
1- draw skeletal structure
2 connect the atoms reasonably
3- add enough bonds to yield S/2=5
4 add enough lone pairs to yield (A-S)/2 =
7 lone pairs
5 make sure all atoms have 8 electrons
(hydrogen to have 2 electrons)
Chapter 05: Periodicity and Atomic Structure
175
Writing Lewis Structures of
Molecules HNO
3
4) Complete octets, outside-in
H is already complete with 2
1 bond
and re-count electrons
N = 5
H = 1
O
3
= 36 = 18
Total = 24 e
-
Electrons
Start 24
Used 8
Left 16
Electrons
Start 16
Used 16
Left 0
Tro, Chemistry: A
Molecular Approach
176
Writing Lewis Structures of
Molecules HNO
3
5) If all octets complete, give
extra electrons to central
atom.
elements with d orbitals can have
more than 8 electrons
Period 3 and below
6) If central atom does not
have octet, bring in
electrons from outside
atoms to share
follow common bonding patterns
if possible
Chapter 05: Periodicity and Atomic Structure
Tro, Chemistry: A
Molecular Approach
177
Practice - Lewis Structures
CO
2
SeOF
2
NO
2
-1
H
3
PO
4
SO
3
-2
P
2
H
4
Tro, Chemistry: A
Molecular Approach
178
Practice - Lewis Structures
CO
2
SeOF
2
NO
2
-1
H
3
PO
4
SO
3
-2
P
2
H
4
:O::C::O:
16 e
-
26 e
-
18 e
-
26 e
-
32 e
-
14 e
-
Chapter 05: Periodicity and Atomic Structure
179
Formal Charge
during bonding, atoms may wind up with more or less
electrons in order to fulfill octets - this results in
atoms having a formal charge
FC = valence e
-
- nonbonding e
-
- bonding e
-
left OFC = 6 - 4 - (4) = 0
S FC = 6 - 2 - (6) = +1
right O FC = 6 - 6 - (2) = -1
sum of all the formal charges in a molecule = 0
in an ion, total equals the charge

O S O

180
Writing Lewis Formulas of Molecules (contd)
7) Assign formal charges to the atoms
a) formal charge = valence e
-
- lone pair e
-
- bonding e
-
0
+1 -1
all 0
Chapter 05: Periodicity and Atomic Structure
181
Practice - Assign Formal Charges
CO
2
SeOF
2
NO
2
-1
H
3
PO
4
SO
3
-2
P
2
H
4
Tro, Chemistry: A
Molecular Approach
182
Practice - Assign Formal Charges
CO
2
SeOF
2
NO
2
-1
H
3
PO
4
SO
3
-2
P
2
H
4
all 0
-1
P = +1
rest 0
S = +1
Se = +1
-1
-1
all 0
-1
-1
-1
Chapter 05: Periodicity and Atomic Structure
183
Resonance
when there is more than one Lewis structure for a molecule
that differ only in the position of the electrons, they are
called resonance structures
the actual molecule is a combination of the resonance forms
a resonance hybrid
look for multiple bonds or lone pairs

O S O O S O

184
Resonance
Chapter 05: Periodicity and Atomic Structure
185
Rules of Resonance Structures
Only electrons can change position
Resonance structures must have the same number
of electrons
Second row elements have a maximum of 8
electrons
Formal charges must total same
Better structures have fewer formal charges
Better structures have smaller formal charges
Better structures have formal charge on more
electronegative atom
186
Exceptions to the Octet Rule
expanded octets
elements with empty d orbitals can have more
than 8 electrons
odd number electron species e.g., NO
will have 1 unpaired electron
free-radical
very reactive
incomplete octets
B, Al
Chapter 05: Periodicity and Atomic Structure
187
Drawing Resonance Structures
-1
-1
+2
0
0
0
Tro, Chemistry: A
Molecular Approach
188
Practice - Identify Structures with
Better or Equal Resonance Forms and
Draw Them
CO
2
SeOF
2
NO
2
-1
H
3
PO
4
SO
3
-2
P
2
H
4
all 0
-1
P = +1
S = +1
Se = +1
-1
-1
all 0
-1
-1
-1
Chapter 05: Periodicity and Atomic Structure
Tro, Chemistry: A
Molecular Approach
189
Practice - Identify Structures with
Better or Equal Resonance Forms and
Draw Them
CO
2
SeOF
2
NO
2
-1
H
3
PO
4
SO
3
-2
P
2
H
4
none
-1
-1
-1
+1
all 0
+1
all 0
-1
none
S = 0
in all
res. forms
Tro, Chemistry: A
Molecular Approach
190
Bond Energies
chemical reactions involve breaking bonds in
reactant molecules and making new bond to
create the products
the AH
reaction
can be calculated by comparing the
cost of breaking old bonds to the profit from
making new bonds
the amount of energy it takes to break one mole
of a bond in a compound is called the bond
energy
in the gas state
homolytically each atom gets bonding electrons
Chapter 05: Periodicity and Atomic Structure
191
Trends in Bond Energies
the more electrons two atoms share, the stronger the
covalent bond
CC (837 kJ) > C=C (611 kJ) > CC (347 kJ)
CN (891 kJ) > C=N (615 kJ) > CN (305 kJ)
the shorter the covalent bond, the stronger the bond
BrF (237 kJ) > BrCl (218 kJ) > BrBr (193 kJ)
bonds get weaker down the column
192
Using Bond Energies to
Estimate AH
rxn
the actual bond energy depends on the
surrounding atoms and other factors
we often use average bond energies to estimate
the AH
rxn
works best when all reactants and products in gas state
bond breaking is endothermic, AH(breaking) = +
bond making is exothermic, AH(making) =
AH
rxn
= (AH(bonds broken)) + (AH(bonds formed))
Chapter 05: Periodicity and Atomic Structure
193
194
Estimate the Enthalpy of the Following
Reaction
Chapter 05: Periodicity and Atomic Structure
Tro, Chemistry: A
Molecular Approach
195
Estimate the Enthalpy of the Following
Reaction
H
2
(g) + O
2
(g) H
2
O
2
(g)
reaction involves breaking 1mol H-H and 1 mol
O=O and making 2 mol H-O and 1 mol O-O
bonds broken (energy cost)
(+436 kJ) + (+498 kJ) = +934 kJ
bonds made (energy release)
2(464 kJ) + (142 kJ) = -1070
AH
rxn
= (+934 kJ) + (-1070. kJ) = -136 kJ
(Appendix AH
f
= -136.3 kJ/mol)
Tro, Chemistry: A
Molecular Approach
196
Bond Lengths
the distance between the nuclei of bonded
atoms is called the bond length
because the actual bond length depends on
the other atoms around the bond we
often use the average bond length
averaged for similar bonds from many
compounds
Chapter 05: Periodicity and Atomic Structure
Tro, Chemistry: A
Molecular Approach
197
Trends in Bond Lengths
the more electrons two atoms share, the shorter
the covalent bond
CC (120 pm) < C=C (134 pm) < CC (154 pm)
CN (116 pm) < C=N (128 pm) < CN (147 pm)
decreases from left to right across period
CC (154 pm) > CN (147 pm) > CO (143 pm)
increases down the column
FF (144 pm) > ClCl (198 pm) > BrBr (228 pm)
in general, as bonds get longer, they also get
weaker
Tro, Chemistry: A
Molecular Approach
198
Bond Lengths
Chapter 05: Periodicity and Atomic Structure
Tro, Chemistry: A
Molecular Approach
199
Metallic Bonds
low ionization energy of metals allows them to lose
electrons easily
the simplest theory of metallic bonding
involves the metals atoms releasing their
valence electrons to be shared by all to
atoms/ions in the metal
an organization of metal cation islands in a sea of
electrons
electrons delocalized throughout the metal structure
bonding results from attraction of cation for the
delocalized electrons
200
Metallic Bonding
Chapter 05: Periodicity and Atomic Structure
201
Metallic Bonding
Model vs. Reality
metallic solids conduct electricity
because the free electrons are mobile, it allows the
electrons to move through the metallic crystal and
conduct electricity
as temperature increases, electrical conductivity
decreases
heating causes the metal ions to vibrate faster,
making it harder for electrons to make their way
through the crystal
Tro, Chemistry: A
Molecular Approach
202
Metallic Bonding
Model vs. Reality
metallic solids conduct heat
the movement of the small, light electrons through
the solid can transfer kinetic energy quicker than
larger particles
metallic solids reflect light
the mobile electrons on the surface absorb the
outside light and then emit it at the same frequency
Chapter 05: Periodicity and Atomic Structure
203
Metallic Bonding
Model vs. Reality
metallic solids are malleable and ductile
because the free electrons are mobile, the direction
of the attractive force between the metal cation
and free electrons is adjustable
this allows the position of the metal cation islands to
move around in the sea of electrons without
breaking the attractions and the crystal structure
204
Metallic Bonding
Model vs. Reality
metals generally have high melting points and
boiling points
all but Hg are solids at room temperature
the attractions of the metal cations for the free
electrons is strong and hard to overcome
melting points generally increase to right across
period
the charge on the metal cation increases across
the period, causing stronger attractions
melting points generally decrease down column
the cations get larger down the column, resulting
in a larger distance from the nucleus to the
free electrons
Chapter 05: Periodicity and Atomic Structure
Valence Bond Theory 01
1. Covalent bonds are formed by overlapping of
atomic orbitals, each of which contains one electron
of opposite spin.
2. Each of the bonded atoms maintains its own atomic
orbitals, but the electron pair in the overlapping
orbitals is shared by both atoms.
3. The greater the amount of orbital overlap, the
stronger the bond.
Covalent bonding
Sigma bonding region of overlap includes the internuclear
axis (line connecting the two atoms)
This type of bonding cannot account for all the molecular
shapes that we find in nature. These orbitals restrict our bond
angles to be 90
o
, 180
o
etc.
Chapter 05: Periodicity and Atomic Structure
Valence Bond Theory 02
Linus Pauling:
Wave functions from s orbitals & p
orbitals could be combined to
form hybrid atomic orbitals. These
hybrid orbitals are made by
combining the mathematical wave
functions of the hydrogenlike
orbitals and dividing them in a way
that they all have the same energy.
This yields orbitals of the desired
orientation
Valence Bond Theory
sp hybrid:
Note that the remaining p
orbital are unhybridized.
They are the same as
before
Arrangement of
hybridized orbitals
is linear
sp hybrid one s
and one p orbital
combine to form
two sp hybrids
s
p p p
p p
sp sp
Chapter 05: Periodicity and Atomic Structure
sp
2
hybrid:
Again note that the
remaining p orbital
remains unhybridized
The arrangement of the
hybridized orbitals is
trigonal planar
s
p p p
p
sp
2
sp
2
hybrid one s
and two p orbitals
combine to form
three sp
2
hybrids
Valence Bond Theory 06
sp
3
hybrid:
Note that all of the s and p orbitals
are hybridized. The d orbitals are
not even pictured but they are still
there if available
Chapter 05: Periodicity and Atomic Structure
Valence Bond Theory 07
sp
3
d hybrid:
Trigonal
Bipyramidal
Valence Bond Theory 08
sp
3
d
2
hybrid:
Octahedral
Chapter 05: Periodicity and Atomic Structure
Valence Bond Theory
The hybridized orbitals determine the electronic
geometry of the central atom.
The unhybridized orbitals may participate in a different
type of bonding called bonding.
In bonding there are two regions of overlap, these are
above and below the internuclear axis
Valence Bond Theory
bonding
These two processes may be occurring
simultaneously and we have a double bond
Chapter 05: Periodicity and Atomic Structure
Valence Bond Theory
This is the valence bond picture of
ethene.
Notice that one of
the bonds is and
the other is .
Valence Bond Theory
As a rule of thumb
A single bond is a bond
A double bond is one bond and one
bond.
A triple bond is one bond and two
bonds.
sp
3
bond
and bonds
sp
2
and bonds
sp
We can tell what the
hybridization is by the number of
regions of high electron density
Chapter 05: Periodicity and Atomic Structure
Valence Bond Theory
Lets practice some bond
types and hybridization
determinations.
How many
bonds are
present?
How many
bonds are
present?
What is the
hybridization on
each atom?
bonds
bonds
H are never
hybridized
Valence Bond Theory
Lets practice some bond
types and hybridization
determinations.
What is the
hybridization on
each atom?
Hs are
never
hybridized
sp
sp
2
Notice that the lone pairs
on the oxygen are not
drawn. We know they are
there otherwise it would
be unstable.
Chapter 05: Periodicity and Atomic Structure
Molecular Orbital Theory
The molecular orbital (MO) model provides a better
explanation of chemical and physical properties than
the valence bond (VB) model.
Atomic Orbital: Probability of finding the
electron within a given region of space in an
atom.
Molecular Orbital: Probability of finding the
electron within a given region of space in a
molecule.
Molecular Orbital Theory
Additive combination of orbitals (o) is lower in energy
than two isolated 1s orbitals and is called a bonding
molecular orbital.
Chapter 05: Periodicity and Atomic Structure
Molecular Orbital Theory
Subtractive combination of orbitals (o
-
) is higher in
energy than two isolated 1s orbitals and is called an
antibonding molecular orbital.
Molecular Orbital Theory
Molecular Orbital Diagram for H
2
:
Chapter 05: Periodicity and Atomic Structure
Molecular Orbital Theory 05
Molecular Orbital Diagrams for H
2

and He
2
:
Molecular Orbital Theory
Additive and subtractive combination of p orbitals leads
to the formation of both sigma and pi orbitals.
Chapter 05: Periodicity and Atomic Structure
Molecular Orbital Theory
Second-Row MO Energy Level Diagrams:
Molecular Orbital Theory
MO Diagrams Can Predict Magnetic Properties:
Chapter 05: Periodicity and Atomic Structure
Molecular Orbital Theory
Bond Order is the number of electron pairs shared
between atoms.
Bond Order is obtained by subtracting the number of
antibonding electrons from the number of bonding
electrons and dividing by 2.
Molecular Orbital Theory
Construct an MO diagram for He
2
+
ion. Determine the
bond order and whether the ion is likely to be stable?
Chapter 05: Periodicity and Atomic Structure
Molecular Orbital Theory
The B
2
and C
2
molecules have MO diagrams similar to
N
2
. What MOs are occupied in B
2
and C
2
, and what is
the bond order in each? Would any of these be
paramagnetic?