Chapter 7

Atomic Structure and Periodicity

7.1 Electromagnetic Radiation 7.9 Polyelectronic Atoms
7.2 The Nature of Matter 7.10 The History of the Periodic
(The Photoelectric Effect) Table
7.3 The Atomic Spectrum of
7.11 The Aufbau Principle and the
Hydrogen
Periodic Table
7.4 The Bohr Model
7.5 The Quantum Mechanical 7.12 Periodic Trends in Atomic
Model of the Atom Properties
(The Physical Meaning of a Ionization Energy Electron
Wave Function) Affinity Atomic Radius
7.6 Quantum Numbers 7.13 The Properties of a Group: The
7.7 Orbital Shapes and Alkali Metals
Energies
7.8 Electron Spin and the Pauli
7.1 Electromagnetic Radiation

Radiant energy that exhibits wavelength-

like behavior and travels through space at
the speed of light in a vacuum.
• Example: The sun light, energy used in
microwave oven, the x-rays used by
doctors.
 Waves
Waves have 3 primary characteristics:
1. Wavelength (): distance between two
consecutive peaks or troughs in a wave.
2. Frequency (): number of waves
(cycles) per second that pass a given point
in space.
3. Speed: speed of light is 2.9979  108
m/s. We will use 3.00 x108 m/s.
The Nature of Waves
 Wavelength and frequency can be interconverted
and they have an inverse relationship
 = c/
 = frequency (s1)
 = wavelength (m)
c = speed of light (m s1)
• Wavelength is also given in nm (1 nm = 10 -9 m)
and Angstroms (Å) (1 Å = 10-10 m).
• The frequency value of s1 or 1/s is also called
“hertz (Hz)” like KHz on the radio.
Classification of Electromagnetic Radiation
Example: When green light is emitted from an
oxygen atom it has a wavelength of 558 nm.
What is the frequency?
We know,
 = c/ where, c = speed of light
8 = 3.00 x 10 8
m/s
3.0 0 1 0 m / s  = wavelength
  7
5.5 8 11 04 m = 558 nm
 5.3 8 1 0 s
1

14
(need
to
9
convert in
m) 5.3 8 1 0 H z 10m 7
5 5 8 nm   5.5 8 1 0 m
1nm
See Exercises 7.31 and 7.32.
 7.2 Nature of Matter
• At the end of nineteenth century, matter thought to
consist of particles, whereas, energy in the form of light
was described as a wave.
• Particles were things that had mass and whose position in
space could be specified.
• Wave were described as massles delocalized, that is,
their position in space could not be specified.
• Planck could account for these observations only by
postulating that energy can be gained or lost only in
whole-number multiples of the quantity h, where h is a
constant called Planck’s constant, determined by
experiment to have the value 6.626x10-34 J s.
 Planck’s Constant
• Transfer of energy is quantized, and can only
occur in discrete units, called quanta.

hc
E = h  =

E = change in energy, in J
h = Planck’s constant, 6.626  1034 J s
 = frequency, in s1
 = wavelength, in m
 Energy and Mass
• Einstein suggested that electromagnetic
radiation can be viewed as a stream of
“particles” called photons.
 Energy and Mass
• According to Einstein theory of relativity-
Energy has mass; Einstein equation,
E = mc2 where, E = energy, m = mass
c = speed of light
• After rearrangement of the equation,
E
m 2
c
Now we can calculate the mass associated
with a given quantity of energy (energy has mass)
• Einstein suggested that electromagnetic radiation
can be viewed as a stream of “particles” called
photons. The energy of each photon is given by,
hc
E p h o to n = h =

E hc /  h
m p h o to n = 2= =
c c 2
c
• It was Einstein who realized that light could not
be explained completely as waves but had to
have particle properties. This is called the dual
nature of light.
Electromagnetic Radiation
 Wavelength and Mass
• De Broglie thought if waves like light could have
particle properties that particles like electrons could
have wave properties. We have,
h h
m  m
c 
  velocity 
de Broglie’s equation, h
 =
m
 = wavelength (m); m = mass (kg);  = velocity (m/s)
h = Planck’s constant, 6.626  1034 J s = kg m2 s1

• This equation allows us to calculate the wavelength of a

particle. Matter exhibits both particulate and wave
properties.
• Example: Compare the wavelength for an electron
(mass = 9.11 x 10-31 kg) traveling at a speed of 1.0 x 10 7
m/s with that for a ball (mass = 0.10 kg) traveling at 35
m/s.
We use the equation  = h/m, where
h = 6.626  1034 J.s or 6.626  1034 kg m2 /s
since, 1 J = 1 kg. m2 /s2
For the electron,  3 4 kg . m . m
6 .6 2 6 1 0
e  s  11
 7 .2 7 1 0 m
9 .11 1 0 kg 1.0 1 0 m / s 
 31 7

For the ball,  34 kg . m . m

6 .6 2 6 1 0  34
b  s  1.9 1 0 m
0 .1 0 kg 3 5 m / s 
 7.3 Atomic Spectrum of Hydrogen
• When H2 molecules absorb energy, some of the H-H
bonds are broken and resulting hydrogen atoms are
excited. The excess energy is released by emitting light of
various wavelengths to produce the emission spectrum of
hydrogen atom.
• Continuous spectrum: Contains all the wavelengths of
light.
Line (discrete) spectrum: Contains only some of the
wavelengths of light. Only certain energies are allowed,
i.e., the energy of the electron in the hydrogen atom is
quantized. hc
E = h  =

A Continuous Spectrum (a) and A Hydrogen Line Spectrum (b)
A Change between Two Discrete Energy Levels
 7.4 The Bohr Model
• The electron in a hydrogen atom moves around the
nucleus only in certain allowed circular orbits. The
energy levels available to the hydrogen atom:
 18 2 2
E =  2.178  10 J ( z / n )
E = energy of the levels in the H-atom
z = nuclear charge (for H, z = 1)
n = an integer, the large the value, the larger is the
orbital radius.
• Bohr was able to calculate hydrogen atom
energy levels that exactly matched the
experimental value. The negative sign in the
above equation means that the energy of the
electron bound to the nucleus is lower than
it would be if the electron were at an
infinite distance.
Electronic Transitions in the Bohr Model for the Hydrogen Atom
• Ground State: The lowest possible energy
state for an atom (n = 1).
• Energy Changes in the Hydrogen Atom
E = Efinal state  Einitial state
 1 1 
= -2.178 x 10-18J 2  2 
 n final n initial 
• The wavelength of absorbed or emitted photon
can be calculated from the equation,
 c hc
E h   =
  E
Example: Calculate the energy required to excite
the hydrogen electron from level n = 1 to level n =
2. Also calculate the wavelength of light that must
be absorbed by a hydrogen atom in its ground state
to reach this excited state.
 18 2 2
Using Equation, E =  2.178  10 J ( z / n ) with Z
= 1 we have

E1 = -2.178 x 10-18 J(12/12) = -2.178 x 10-18 J

E2 = -2.178 x 10-18 J(12/22) = -5.445 x 10-19 J

E = E2 - E1 = (-5.445 x 10-19 J) – (-2.178 x 10-18 J)

-18
The positive value for E indicates that the system
has gained energy. The wavelength of light that
must be absorbed to produce this change is

(6.626 x 10-34 J.s)(2.9979 x 108 m/s)

hc 1.633 x 10 -18
J
  
E = 1.216 x 10-7 m

See Exercises 7.45 and 7.46.

See Exercises 7.51 and 7.52.
Example: Calculate the energy required to remove
the electron from a hydrogen atom in its ground
state.
Removing the electron from a hydrogen atom in its
ground state corresponds to taking the electron
from ninitial = 1 to nfinal = . Thus,

 1 1 
E = -2.178 x 10 J  2  2
-18

 n final n initial 
 1 1
= -2.178 x 10 J   12
-18  
The energy required to remove the electron from a
hydrogen atom in its ground state is 2.178 x 10 -18 J.
 7.5 Quantum Mechanics
Based on the wave properties of the atom
Schrodinger’s equation is (too complicated to be
detailed here),
H = E 
 = wave function
H = mathematical operator
E = total energy of the atom
A specific wave function is often called an orbital.
This equation is based on operators – not simple
algebra. This is a mathematical concept you will
not have dealt with yet.
 Heisenberg Uncertainty Principle
h
 x  m v  
x = position 4
mv = momentum
h = Planck’s constant
The more accurately we know a particle’s
position, the less accurately we can know its
momentum. Both the position and momentum
of a particle can not be determined precisely
at a given time. The uncertainty principle
implies that we cannot know the exact motion
of the electron as it moves around the nucleus.
Radial Probability Distribution
 7.6 Quantum Numbers (QN)
When we solve the Schrodinger equation, we find many
wave functions (orbitals) that satisfy it. Each of these
orbitals is characterized by a series of numbers called
quantum numbers, which describe various properties of
the orbital.
1. Principal QN (n = 1, 2, 3, . . .) - related to size and
energy of the orbital.
2. Angular Momentum QN (ℓ= 0 to n  1) - relates to
shape of the orbital. ℓ = 0 is called s; ℓ= 1 is called p; ℓ= 2
is called d; ℓ = 3 is called f.
3. Magnetic QN (mℓ = l to l including 0) - relates to
orientation of the orbital in space relative to other orbitals.
4. Electron Spin QN (ms = +1/2, 1/2) - relates to the spin
states of the electrons.
Example: For principal quantum level n = 5,
determine the number of allowed subshells
(different values of ℓ), and give the designation of
each.
For n = 5, the allowed values of ℓ run from 0 to 4 (n
– 1 = 5 – 1). Thus the subshells and their
designations are

ℓ=0 ℓ=1 ℓ=2 ℓ=3 ℓ=4

5s 5p 5d 5f 5g

See Exercises 7.57 through 7.59.

 7.7 Orbital Shapes and Energies
Two types of representations for the hydrogen 1s,
2s and 3s orbitals are shown below. The s orbitals
are spherical shape.

Two Representations of the

Hydrogen 1s, 2s, and 3s Orbitals
 Representation of p orbitals
The p orbitals are not spherical like s orbital but have two
lobes separated by a node at the nucleus. The p orbitals are
labeled according the axis of the xyz coordinate system.

The Boundary Surface Representations of All Three 2p Orbitals

 Representation d orbitals
The five d orbital shapes are shown below. The d
orbitals have two different fundamental shapes.

The Boundary Surfaces of All of the 3d Orbitals

 Energy Diagram for Hydrogen Atom
The energy of a particular orbital is determined by its value
of n. All orbitals with the same value of n have the same
energy and are said to be degenerate. Hydrogen single
electron occupy the lowest energy state, the ground state.
If energy is put into the system, the electron can be
transferred to higher energy orbital called excited state.

Orbital Energy
Levels for the
Hydrogen Atom
 7.8 Electronic spin and Pauli Exclusion
Principle

• In a given atom, no two electrons can have the

same set of four quantum numbers (n, ℓ, mℓ, ms).
• Since electrons in the same orbital have the same
values of n, ℓ , and mℓ, this postulate says that
they must have different values of ms.
• Therefore, an orbital can hold only two
electrons, and they must have opposite spins.
 7.9 Polyelectronic Atoms
• For polyelectronic atoms in a given principal
quantum level all orbital are not in same energy
(degenerate). For a given principal quantum level
the orbitals vary in energy as follows:

Ens< Enp < End < Enf

• In other words, when electrons are placed in a

particular quantum level, they prefer the orbital in
the order s, p, d and then f.
7.11 Aufbau Principle and the Periodic
Table
As protons are added one by one to the nucleus
to build up the elements, electrons are similarly
added to these hydrogen-like orbitals.
 Hund’s Rule
The lowest energy configuration for an atom is
the one having the maximum number of
unpaired electrons allowed by the Pauli
principle in a particular set of degenerate
orbitals.

N : 1s2 2s2 2p3, O : 1s2 2s2 2p4,

F : 1s2 2s2 2p5, Ne : 1s2 2s2 2p6,
Na : 1s2 2s2 2p63s1 OR [Ne] 3s1
The elements in the same group (vertical column of the
periodic table) have the same valence electron
configuration.
Elements with the same valence electron configuration show
similar chemical behavior.

The Electron Configurations in the Type of Orbital Occupied

Last for the First 18 Elements
 Valence Electrons
The electrons in the outermost principle quantum
level of an atom.
Atom Valence Electrons
Ca 2
N 5
Br 7
Valence electron is the most important electrons
to us because they are involved in bonding.
Elements with the same valence electron
configuration show similar chemical behavior.
Inner electrons are called core electrons.
Electron Configurations for Potassium Through Krypton
The Orbitals Being Filled for Elements in Various Parts of the Periodic Table
The Periodic Table With Atomic Symbols, Atomic
Numbers, and Partial Electron Configurations
 Broad Periodic Table Classifications

• Representative Elements (main group): filling s

and p orbitals (Na, Al, Ne, O)
• Transition Elements: filling d orbitals (Fe, Co, Ni)
• Lanthanide and Actinide Series (inner transition
elements): filling 4f and 5f orbitals (Eu, Am, Es)
The Order in which the Orbitals Fill in Polyelectronic Atoms
 7.12 Periodic Trends

1. Ionization energy
2. Electron affinity and,
3. Atomic size:
 Ionization Energy
The quantity of energy required to remove an
electron from the gaseous atom or ion.

X(g) X+ (g) + e-
where, the atom or ion is assumed to be in its
ground state.
Ionization energy increases from left to right across a period;
decreases going down a group
The Values of First Ionization Energy for
The Elements in the First Six Periods
Trends in Ionization Energies
for the Representative Elements
In a stepwise ionization
process, it is always the
highest-energy electron (the
one bound least tightly) that is
removed
first. “first ionization energy
I1 “
The value of I1 is considerably
smaller than the value of I2 ,
the second ionization energy
The primary factor is simply I4 corresponds to removing
charge.
The first electron is removed a core electron (Al3+ has
from a 3p orbital that is higher the configuration
in energy than the 3s orbital 1s22s22p6), and core
from which the second electron electrons are bound much
is removed. more tightly than valence
electrons
 Electron Affinity

The energy change associated with the addition

of an electron to a gaseous atom.
X(g) + e  X(g)
These values tend to be exothermic (energy
released). Adding an electron to an atom causes it
to give off energy. So the value for electron
affinity will carry a negative sign.
The Electronic Affinity Values for Atoms Among the
First 20 Elements that Form Stable, Isolated X - Ions
 Periodic Trends
Atomic Radii: Atomic radii can be obtained by
measuring the distances between atoms in chemical
compounds and atomic radius is assumed to be half
this distance.
• Decrease going from left to right across a period.
This decrease can be explained in terms of the
increasing effective nuclear charge in going from
left to right. The valence electron are drawn closer
to the nucleus, decreasing the size of the atom.
• Increase going down a group, because of the
increase in orbital sizes in successive principal
quantum levels.
The Radius of an Atom
Atomic Radii for Selected Atoms
 Information Contained
in the Periodic Table
1. Each group member has the same valence electron
configuration. Group elements exhibit similar chemical
properties.
2. The electron configuration of any representative element can
be obtained from periodic table. Transition metals – two
exceptions, chromium and copper.
3. Certain groups have special names (alkali metals, halogens,
etc).
4. Metals and nonmetals are characterized by their chemical
and physical properties. Many elements along the division
line exhibit both metallic and non metallic properties
which are called metalloids or semimetals.
Special Names for Groups in the Periodic Table
 Summary
• Electromagnetic Radiation: Wavelength like
behavior.
• Frequency,  = c/( = wavelength, c = speed of
light).
• Energy Transfer, E = h = hc/
• de Broglie’s Equation:  = h/m
• The Bohr Model: electron in a hydrogen atom moves
around the nucleus only in certain allowed circular
orbits.
• Quantum Mechanics: H= E
• Heisenberg Uncertainty Principle: Position and
momentum cannot be determined precisely at a given
time.
• Quantum Numbers: Principal QN, Angular
momentum QN, Magnetic QN, an Electron Spin
QN.
• Orbital Shapes and Energies: s, p, and d orbitals.
• Pauli Exclusion Principle:
• Aufbau Principle:
• Hund’s Rule:
• Periodic Table:
• Ionization Energy:
• Electron Affinity:
• Periodic Trends: