9/1/2022

Chapter 6:
Light and Electronic
Structure

Energy and Energy Changes

Energy is the capacity to do work or transfer heat.

All forms of energy are either kinetic or potential.

Kinetic energy (Ek) is the energy of motion.

1 m is the mass of the object
𝐸k = 𝑚𝑢2
2 u is its velocity
One form of kinetic energy of interest to chemists is thermal energy, which is the energy
associated with the random motion of atoms and molecules.

Potential energy is the energy possessed by an object by virtue of its position.

There are two forms of potential energy of great interest to chemists:

Chemical energy is energy stored within the structural units of chemical substances.
Electrostatic energy is potential energy that results from the interaction of charged
particles.
𝑄1 𝑄2 Q1 and Q2 represent two charges
𝐸el = 2
𝑑 separated by the distance, d.

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Energy and Energy Changes

Kinetic and potential energy are interchangeable – one can be converted to the other.

Although energy can assume many forms, the total energy of the universe is constant.
• Energy can neither be created nor destroyed.
• When energy of one form disappears, the same amount of energy reappears in another
form or forms.
• This is known as the law of conservation of energy.

A diver:
Has Ep due to macroscale position.
Converts Ep to macroscale Ek.
Converts Ek,macroscale to Ek,nanoscale
(motion of water, heat)

Practice
Water in a damned-up lake :
Potential
Water rushing through turbines:
Kinetic
Moving baseball:
Kinetic
Diver standing on a cliff:
Potential
Gallon of gas:
Potential (chemical)

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Units of Energy
The SI unit of energy is the joule (J), named for the English physicist James Joule. A Joule is the
amount of energy possessed by a 2–kg mass moving at a speed of 1 m/s.

1 1 1m 2 𝟏 𝐤𝐠 ∙𝐦𝟐
Ek = 𝑚𝑢2 = 2 kg = =𝟏𝐉
2 2 s 𝐬𝟐

The joule can also be defined as the amount of energy exerted when a force of 1 newton (N) is
applied over 1 meter.
1J=1N·m
Because the magnitude of a joule is so small, we often express large amounts of energy using the
unit kilojoule (kJ).
1 kJ = 1000 J

calorie (cal)
Originally: “The energy needed to heat of 1g of water from 1°C.”
Now: 1 cal = 4.184 J (exactly)

Dietary Calorie (Cal) – the “big C” calorie. Used on food products. 5

1 Cal = 1000 cal = 1 kcal

The Nature of Light

Visible light is only a small component of
the continuum of radiant energy known
as the electromagnetic spectrum.

All forms of electromagnetic radiation travel in [Link] are characterized

by:
Wavelength (λ) – the distance between identical points on successive waves
Frequency (ν) – the number of waves that pass through a point in 1 second.
Amplitude – the vertical distance from the midline of a wave to the top of the
peak or the bottom of the trough.

An electromagnetic wave has both an

electric field component and a magnetic
component.

The electric and magnetic components have 6

the same frequency and wavelength.

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The Double–Slit Experiment

When light passes through two closely spaced slits, an interference pattern is produced.

Constructive interference is a result of adding

waves that are in phase.

Destructive interference is a result of adding

waves that are out of phase.

This type of interference is typical of waves and demonstrates the wave nature of light.

The speed of light (c) through a vacuum is a constant: c = 2.998 x108 m s–1.
Speed of light, frequency and wavelength are related:
𝜆 is expressed in meters
𝒄 = 𝝀𝝂 𝜈 is expressed in reciprocal seconds (s–1)
s–1 is also known as hertz (Hz)

Practice
(a) What is the frequency of radiation with a wavelength of 280 nm? (b) What is the wavelength
of light with a frequency of 5.65 x 1014 Hz?
a) c = 2.998 x 108 m s–1 so our units must be in m and seconds. The 280 nm must be converted
to meters. 280 nm 1 𝑥 10−9 m
= 2.80 𝑥 10−7 m
𝑐 = 𝜆𝜈 1 nm

𝑐 2.998 𝑥 108 m s−1

𝜈= = = 1.07 𝑥 1015 s−1
𝜆 2.80 𝑥 10−7 m

b) 𝑐 = 𝜆𝜈
𝑐 2.998 𝑥 108 m s−1
𝜆= = = 5.31 𝑥 10−7 m = 531 nm
𝜈 5.65 𝑥 1014 s−1

What is the frequency for 500. nm light?

𝑐 2.998 𝑥 108 m s−1
𝜈= = = 6.0 x 1014 Hz
𝜆 500 𝑥 10−9 m

Assume a microwave oven operates at a frequency of 1.80 x 1011 s–1. What is the wavelength?
𝑐 2.998 𝑥 108 m s−1
𝜆= = = 1.67 𝑥 10−3 m = 1.67 𝑥 106 nm
𝜈 1.80 𝑥 1011 𝑠 −1
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Practice
What is the wavelength of light if the frequency is 2.86 x 10 14 s–1? Where does this wavelength
fall in the EM spectrum?

What is the frequency of light with a wavelength of 366 nm?

A. 8.17 x 105 s–1

B. 1.09 x 1020 s–1
C. 8.17 x 10-4 s–1
D. 8.17 x 1014 s–1

Quantum Theory
Early attempts by nineteenth-century physicists to figure out the structure of the atom met with
only limited [Link] were using the laws of classical physics. These laws describe the
behavior of macroscopic objects.

Over time, the realization and acceptance was the behavior of subatomic particles is NOT
governed by the same physical laws as larger objects. This became known as Quantum
Mechanics.

10
Ramp (“classical”) & stairs (quantized)

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Quantization of Energy
When a solid is heated, it emits electromagnetic radiation, known as blackbody radiation,
over a wide range of wavelengths. The amount of energy given off at a certain temperature
depends on the wavelength. Classical physics assumed that radiant energy was continuous; that
is, could be emitted or absorbed in any amount.

Max Planck suggested that radiant energy is only emitted or absorbed in discrete quantities, like
small packages or bundles. A quantum of energy is the smallest quantity of energy that can be
emitted (or absorbed).

The energy E of a single quantum of energy is

𝑬 = 𝒉𝝂 h : Planck’s constant: 6.626 x10–34 J∙s
The idea that energy is quantized rather than continuous is like walking up a staircase or playing
the [Link] cannot step or play anywhere (continuous), you can only step on a stair or play on
a key (quantized).

Einstein proposed that the beam of light is really a stream of particles. These “particles” of light
are now called photons.
𝒄 𝒉𝒄 11
𝒄 = 𝝀𝝂 𝝂= 𝑬 = 𝒉𝝂 𝑬=
𝝀 𝝀

11

Practice
Calculate the energy (in joules) of (a) a photon with a wavelength of 501 nm and (b) a photon
with a wavelength of 50.1 nm.
(a) 𝐸 = ℎ𝑐 = 6.63 𝑥 10−34 J∙s 2.998 𝑥 108 m s−1 ℎ𝑐 6.63 𝑥 10−34 J∙s 2.998 𝑥 108 m s−1
𝜆
(b) 𝐸 = =
501 𝑥 10−9 m 𝜆 50.1 𝑥 10−9 m
𝐸 = 3.97𝑥 10−19 J 𝐸 = 3.97𝑥 10−18 J

What is the energy of a photon at 379. nm?

ℎ𝑐 6.63 𝑥 10−34 J∙s 2.998 𝑥 108 m s−1
𝐸=
𝜆
= = 5.24𝑥 10−19 J
379 𝑥 10−9 m

What is the energy of a photon of frequency 4.86 x 10 11 s-1?

𝐸 = ℎν = 6.63 x 10−34 J ∙ s 4.86 x 1011 s−1 = 3.22 x 10−22 J

What is the frequency of light having an energy of 1.93 x 10–17 J

𝐸 1.93 𝑥 10−17 J
ν= = = 2.91 𝑥 1016 𝐻𝑧
ℎ 6.63 𝑥 10−34 J∙s

The nitrogen laser emits light at 337.1 nm. What is the energy of this light?
12
ℎ𝑐 6.63 𝑥 10−34 J∙s 2.998 𝑥 108 m s−1
𝐸= = = 5.90 𝑥 10−19 J
𝜆 337.1 𝑥 10−9 m

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Bohr’s Theory of the Hydrogen Atom

The emission spectrum of a substance can be seen by energizing a sample
of material with some form of energy.

The “red hot” or “white hot” glow of an iron bar removed from a fire is the
visible portion of its emission spectrum.

The emission spectrum of both sunlight and a heated solid are continuous; all
wavelengths of visible light are present.

Line spectra
are the
emission of
light only at
specific
wavelengths.
Every element
has its own
unique
emission
spectrum. 13

13

Atomic Line Spectra

The Rydberg equation can be used to calculate the wavelengths of the four visible lines in the
emission spectrum of HYDROGEN.

1 1 1 R∞ :Rydberg constant (1.09737317 x 107 m–1)

= 𝑅∞ 2 − 2 λ the wavelength of a line in the spectrum of hydrogen
𝜆 𝑛1 𝑛2
n1 and n2 are positive integers where n2 > n1.
1 1 ni (initial state) and nf (final state)
∆𝐸 = −2.18 𝑥 10−18𝐽 2− 2 ∆E negative (photon emitted: energy lost to
𝑛f 𝑛i surroundings); positive (photon absorbed)

Bohr’s theory explains the line spectrum of the hydrogen atom. Radiant energy absorbed by the
atom causes the electron to move from the ground state (n = 1) to an excited state (n > 1).

Conversely, radiant energy is emitted when the electron moves from a higher–energy state to a
lower–energy excited state or the ground state.

The quantized movement of the electron from one energy state to another
14
is analogous to a ball moving and down steps.

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The Line Spectrum of Hydrogen

Neils Bohr attributed the emission of radiation by an energized hydrogen atom to the electron
dropping from a higher–energy orbit to a lower one.

As the electron dropped, it gave up a quantum of energy in the form of light.

Bohr showed that the energies of the electron in a hydrogen atom are given by the equation:

1 En energy
𝐸n = −2.18 𝑥 10−18 J
𝑛2 n a positive integer

As an electron gets closer to the nucleus, n decreases. En becomes larger in absolute value
(more negative) as n gets smaller.

En is most negative when n = 1.

Called the ground state, the lowest energy state of the atom
For hydrogen, this is the most stable state

The stability of the electron decreases as n increases. 15

Each energy state in which n > 1 is called an excited state.

15

The Line Spectrum of Hydrogen

1 1
∆𝐸 = −2.18 𝑥 10−18 J −
𝑛f2 𝑛i2
Emission Series in the Hydrogen Spectrum
Series nf ni Spectrum Region
Lyman 1 2,3,4,…. Ultraviolet (UV)
Balmer 2 3,4,5,…. Visible and UV
Paschen 3 4,5,6,…. Infrared
Brackett 4 5,6,7…. Infrared

Calculate the wavelength (in nm) of the photon emitted when an electron transitions from the n
= 4 state to the n = 3 state in a hydrogen atom. ℎ𝑐 ℎ𝑐
1 1 𝐸= 𝜆=
𝜆 𝐸
∆𝐸 = −2.18 𝑥 10−18 J −
𝑛f2 𝑛i2 6.63 𝑥 10−34 J ∙ s 2.998 𝑥 108 m s −1
1 1 𝜆= = 1.88 𝑥 10−6 m
∆𝐸 = −2.18 𝑥 10−18 J − 1.060 𝑥 10−19 J
32 42
1.88 𝑥 10−6 m 1 nm
∆𝐸 = −1.060 𝑥 10−19 J = 1880 nm
1.0 𝑥 10−9 m
𝐸 = 1.060 𝑥 10−19 J 16

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Practice
Calculate the ΔE and wavelength (in nm) for an H–atom undergoing an n = 4 to n = 2 transition.
1 1 6.63 𝑥 10−34 J ∙ s 2.998 𝑥 108 m s−1
∆𝐸 = −2.18 𝑥 10−18 J − = −4.086 𝑥 10−19 J 𝜆=
22 42 4.086 𝑥 10−19 J
𝜆 = 4.862 𝑥 10−7 m
𝐸 = 4.086 𝑥 10−19 J
4.862 𝑥 10−7 m 1 nm
ℎ𝑐 ℎ𝑐 = 486.2 nm
𝐸= 𝜆= 1.0 𝑥 10−9 m
𝜆 𝐸
Calculate the wavelength emitted with an electron changes from n = 6 to n = 2 in the H atom.
What is the Energy for that photon?
1 1
∆𝐸 = −2.18 𝑥 10−18 J − = −4.84 𝑥 10−19 J
22 62

𝐸 = 4.086 𝑥 10−19 J

What is energy (in kJ) for 1 mole of those photons?

4.086 x 10−19 J 6.022 x 1023 photons 291732.44 J
=
photon 1 mol 1 mol

291.7 k J 17
E=
mol

17

Wave Properties of Matter

Louis de Broglie reasoned that if light can behave like a stream of particles (photons), then
electrons could exhibit wavelike properties.

According to de Broglie, electrons behave like standing waves.

Only certain wavelengths are allowed.

At a node, the amplitude of the wave is zero.

De Broglie deduced that the particle and wave properties are

related by the following expression:

ℎ λ is the wavelength associated with the particle

𝜆= m is the mass (in kg)
𝑚𝑢 u is the velocity (in m/s)

The wavelength calculated from this equation is known as the de Broglie

wavelength. 18

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Practice
Calculate the de Broglie wavelength of the “particle,” when considering a 10.0 g bullet traveling
at 762 m/s.

ℎ 6.63 𝑥 10−34 kg
𝜆= ℎ = 6.63 𝑥 10−34 J =
𝑚𝑢 m2 s

10.0 g 1 kg
= 0.0100 kg
1000 g

6.63 𝑥 10−34 kg
ℎ m2 s
𝜆= = = 8.70 𝑥 10−35 m
𝑚𝑢 762 m
0.0100 kg
s

19

19

Electron diffraction
Diffraction of Electrons pattern of aluminum foil.

Experiments have shown that electrons do indeed possess wavelike

properties:
The Heisenberg uncertainty principle states that it is impossible to
know simultaneously both the momentum p and the position x of a particle
with certainty.
ℎ Δx is the uncertainty in position in meters
Δ𝑥 ∙ Δ𝑝 ≥ Δp is the uncertainty in momentum
4𝜋
ℎ Δu is the uncertainty in velocity in m/s
Δ𝑥 ∙ 𝑚Δ𝑢 ≥ m is the mass in kg
4𝜋
An electron in a hydrogen atom is known to have a velocity of 4.99×106 m/s + 5 percent. Using the
uncertainty principle, calculate the minimum uncertainty in the position of the electron. (the mass of an
electron is 9.11 x 10–31 kg)
ℎ 0.05 5.0 𝑥 106 m 2.5 𝑥 105 m
Δ𝑥 ∙ 𝑚Δ𝑢 ≥ ∆𝑢 = =
4𝜋 s s
ℎ
Δ𝑥 ≥
4𝜋 ∙ 𝑚Δ𝑢
6.63 𝑥 10−34 kg ∙ m2
s 𝜟𝒙 ≥ 𝟐. 𝟑 𝒙 𝟏𝟎−𝟏𝟎 𝐦 20
Δ𝑥 ≥
2.5 𝑥 105m
4𝜋 ∙ 9.11 𝑥 10−31 kg
𝑠
20

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The Schrödinger Equation and The Quantum

Mechanical Description of the H–Atom
Erwin Schrödinger derived a complex mathematical formula to incorporate
the wave and particle characteristics of [Link] behaviour is
described with the wave function ψ.
The probability of finding an electron in a certain area of space is
proportional to ψ2 and is called electron density.
Probability map of an
Quantum Mechanics defines the region where the electron is most electron in an H atom
likely to be at a given time

The Schrödinger equation specifies possible energy states an

electron can occupy in a hydrogen atom.

The energy states and wave functions are characterized by a

set of quantum numbers.

Instead of referring to orbits as in the Bohr model, quantum

numbers and wave functions describe atomic orbitals. 21

21

Quantum Numbers
Quantum numbers are required to describe the distribution of electron density in an atom
(location of the electron.)

There are three quantum numbers necessary to describe an atomic orbital.

The principal quantum number (n) – designates size
Larger values of n correspond to larger orbitals (higher energy).
The allowed values of n are integral numbers: 1, 2, 3 and so forth.
The value of n corresponds to the value of n in Bohr’s model of the hydrogen atom.
A collection of orbitals with the same value of n is frequently called a shell.
The angular moment quantum number (l) – describes shape
The values of l are integers that depend on the value of the principal quantum number
The allowed values of l range from 0 to n – 1. Example: If n = 2, l can be 0 or 1.
l 0 1 2 3
Orbital Designation (Shape) s p d f
A collection of orbitals with the same value of n and l is referred to as a subshell.
The magnetic quantum number (ml) – specifies orientation/direction
The values of ml are integers that depend on the value of the angular moment quantum number:
– l,…0,…+l
22

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Atomic Orbitals
All s orbitals are spherical: One orientation:
l =0
ml =0
angular momentum quantum
principal quantum
2s number (l = 0)
number (n = 2)
ml = 0; only 1 orientation possible

p orbitals are dumbbell shaped: Three orientations:

l =1
ml = –1, 0, +1

d orbitals: Five orientations:

l =2
ml = –2, –1, 0, +1, or +2

23

23

Quantum Numbers
Allowed Values of the Quantum Numbers n, l, and ml
n l can be When l is ml can be
1 Only 0 0 Only 0
0 Only 0
2 0 or 1 Quantum
1 –1, 0, or +1 numbers
0 Only 0 designate
3 0, 1, or 2 1 –1, 0, or +1 shells,
subshells, and
2 –2, –1, 0, +1, +2
orbitals.
0 Only 0
1 –1, 0, or +1
4 0, 1, 2, or 3
2 –2, –1, 0, +1, +2
3 –3, –2, –1, 0, +1, +2, +3

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Atomic Orbitals
The electron spin quantum number (ms ) is used to specify an
electron’s spin. There are two possible directions of spin. Allowed
values of ms are +½ and –½.

To summarize quantum numbers:

principal (n) – size
angular (l ) – shape
magnetic (ml) – orientation
electron spin (ms) direction of spin

Angular
Principal (n=2) Momentum (l =1)

2px
Related to the Magnetic 25
Quantum (ml =1)

25

Practice
What are the possible values for the magnetic quantum number (m l) when the principal quantum number
(n) is 2 and the angular quantum number (l) is 0? ml = 0

List the values of n, l, and ml for each of the orbitals in a 2p subshell.

n=2 l=1 ml = –1, 0, +1

Which of the following is a legitimate set of quantum numbers for n, l, and ml respectively, which
corresponds to an 5f orbital?
A. 5, 4, –4 B. 3, 3, – 1 C. 5, 4, 0 D. 5, 3, 0

Which of the following is a list of allowed quantum numbers for an electron?

A. n = 1, l = 1, ml = 0, ms = ½
B. n = 2, l = 0, ml = 1, ms = ½
C. n = 3, l = 0, ml = 0, ms = ½
D. n = 4, l = 3, ml = 4, ms = –½
26

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Practice
List one set of valid quantum numbers for an electron found in each of the following atomic
shells.
2s

2p

3p

4d

5f

27

27

Electron Configurations
General rules for writing electron configurations:
1. Electrons will reside in the available orbitals of the lowest possible energy.
2. Each orbital can accommodate a maximum of two electrons. Up-Side Down
3. Electrons will not pair in degenerate orbitals if an empty orbital is available. Christmas Tree
4. Orbitals will fill in the order indicated in the figure.

Periodic Table Method

28

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Electron Configurations
The electron configuration describes how the electrons are distributed in the various atomic
orbitals.

In a ground state hydrogen atom, the electron is found in the 1s orbital.

Ground state electron

2s 2p 2p 2p
Energy

configuration of hydrogen
principal 1s1 number of electrons in
(n = 1) the orbital or subshell
↿ The use of an up arrow indicates
an electron with ms = + ½
angular
momentum (l = 0)
1s

29

29

Electron Configurations
If hydrogen’s electron is found in a higher energy orbital, the atom is in an excited state.

Possible excited state electron

↿ configuration of hydrogen.
2s 2p 2p 2p 2s1
Energy

1s
The helium emission spectrum is more complex than the hydrogen [Link] are more
possible energy transitions in a helium atom because helium has two electrons.

30

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Electron Configurations
In a multi-electron atoms, the energies of the atomic orbitals are split.

4d 4d 4d 4d 4d
5s
4p 4p 4p
3d 3d 3d 3d 3d Splitting of energy levels refers to the
4s splitting of a shell (n=3) into subshells
3p 3p 3p of different energies (3s, 3p, 3d)
3s
Energy

2p 2p 2p
2s

1s
31

31

Electron Configurations
According to the Pauli exclusion principle, no two electrons in an atom can have the same
four quantum numbers.
The Aufbau principle states that electrons are added to the lowest energy orbitals first before
moving to higher energy orbitals.

The ground state electron The ground state electron

configuration of He (2 e–) configuration of Li (3 e–)
1s2 1s22s1

2p 2p 2p ↿ 2p 2p 2p
2s
Energy

2s
Energy

The 3rd e– must go in the

The 2nd e– has the next available orbital with
the lowest possible energy
↿⇂ same n, l, and ml but
ms is opposite in sign. ↿⇂
1s 1s 32

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Electron Configurations
The Aufbau principle states that electrons are added to the lowest energy orbitals first before
moving to higher energy orbitals.

The ground state electron The ground state electron

configuration of Be (4 e–) configuration of B (5 e–)
1s22s2 1s22s22p1

↿
↿⇂ 2p 2p 2p ↿⇂ 2p 2p 2p
2s 2s

Energy
Energy

↿⇂ ↿⇂
1s 1s
33

33

Electron Configurations
According to Hund’s rule, the most stable arrangement of electrons is the one in which the
number of electrons with the same spin is maximized.

The ground state electron The ground state electron

configuration of C (6 e–) configuration of N (7 e–)
1s22s22p2 1s22s22p3

↿ ↿ ↿ ↿ ↿
↿⇂ 2p 2p 2p ↿⇂ 2p 2p 2p
2s 2s
Energy

Energy

The 2p orbitals are of equal

↿⇂ energy, or degenerate.
↿⇂
1s Put 1 electron in each 1s
34
before pairing (Hund’s rule).

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Electron Configurations
According to Hund’s rule, the most stable arrangement of electrons is the one in which the
number of electrons with the same spin is maximized.

When there are one or more unpaired electrons, as in the case of oxygen and fluorine, the atom
is called paramagnetic.

The ground state electron The ground state electron

configuration of O (8 e–) configuration of F (9 e–)
1s22s22p4 1s22s22p5

↿⇂ ↿ ↿ ↿⇂ ↿⇂ ↿
↿⇂ 2p 2p 2p ↿⇂ 2p 2p 2p
2s 2s
Energy

Energy
Once all the 2p orbitals
are singly occupied,
↿⇂ additional electrons will
have to pair with those
↿⇂
1s already in the orbitals.
1s
35

35

Electron Configurations

When all electrons in an atom are paired, as in neon, it is called diamagnetic.

The ground state electron

configuration of Ne (10 e–)
1s22s22p6

↿⇂ ↿⇂ ↿⇂
↿⇂ 2p 2p 2p
2s
Energy

↿⇂
1s

36

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Practice
Write the electron configuration and give the orbital diagram of Fe (Z = 26) and Ar (Z = 18).
Fe 1s22s22p63s23p64s23d6
Ar 1s22s22p63s23p6
The 7 electrons in Nitrogen are found in the following atomic shells. List the quantum numbers for each
electron.
1s (2 electrons) n = 1, l = 0, ml = 0, ms= +1/2 n = 1, l = 0, ml = 0, ms= –1/2
2s (2 electrons) n = 2, l = 0, ml = 0, ms= +1/2 n = 2, l = 0, ml = 0, ms= –1/2

2p (3 electrons) n = 2, l =1, ml = –1, ms= +1/2

n = 2, l =1, ml = 0, ms= +1/2
n = 2, l =1, ml = +1 ms= +1/2
Which of the following electron configurations represents silicon?
A. 1s22s22p63s33p2
B. 1s22s32p63s23p2
C. 1s22s22p63s23p2
D. 1s22s22p63s23p4 37

37

Practice
Write the electron configuration for the following elements:

Mg 1s22s22p63s2 Ba 1s22s22p63s23p64s23d104p65s24d105p66s2
P 1s22s22p63s23p2 V 1s22s22p63s23p64s23d3
Ni 1s22s22p63s23p64s23d8 Sr 1s22s22p63s23p64s23d104p65s2
Ag 1s22s22p63s23p64s23d104p65s14d10 W 1s22s22p63s23p64s23d104p65s24d105p66s24f145d4
Pb 1s22s22p63s23p64s23d104p65s24d105p66s24f145d106p2 O 1s22s22p4

What is the correct electron configuration for sulfur?

A. 1s22s22p63s23p5
B. 1s22s22p63s23p4
C. 1s22s22p73s23p2
D. 3s23p4
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Electron Configurations and the Periodic

Table
The electron configurations of all elements except hydrogen and helium can be represented
using a noble gas core. These core electrons are highly stable. Those not in the core are
considered valence electrons.

The electron configuration of potassium (Z = 19) is 1s22s22p63s23p64s1. Ar has an electron

configuration of 1s22s22p63s23p6, allowing us to simplify potassium’s configuration to [Ar]4s1.
Ground State Electron Configuration of K:
1s22s22p63s23p64s1

[Ar]
Noble Gas Configuration of K:
[Ar]4s1

Give the noble gas configuration for the following:

Ba [Xe]6s2

Hg [Xe]6s24f145d10
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Fe [Ar]4s23d6
39

Electron Configurations and the Periodic

Table
There are several notable exceptions to the order of electron filling for some of the transition
metals.

The reason for these anomalies is the slightly greater stability of d subshells that are either half-
filled (d5) or completely filled (d10).

Copper (Z = 29) is [Ar]4s13d10 and NOT [Ar]4s23d9 as expected.

Cu: [Ar] ↿ ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂
4s 3d 3d 3d 3d 3d

Chromium (Z = 24) is [Ar]4s13d5 and NOT [Ar]4s23d4 as expected.

Cr: [Ar] ↿ ↿ ↿ ↿ ↿ ↿
4s 3d 3d 3d 3d 3d

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Diamagnetic and Paramagnetic

Spinning e– = tiny magnet. If all e– are paired, then the magnets cancel.
The atom is diamagnetic and is pushed weakly away from magnetic fields.

With unpaired e–:

Unpaired spins point in the same direction (Hund’s rule) making the magnets add together.
The atom is paramagnetic and are attracted to magnetic fields.

If individual atom-magnets line up in a bulk sample

A ferromagnet – a permanent magnet.

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Diamagnetic and Paramagnetic

For each of the atoms/ions below, draw out the electrons with energy levels and determine if it
would be diamagnetic or paramagnetic. How many unpaired electrons?

Ca N F
↿⇂ Diamagnetic Paramagnetic Paramagnetic

4s
↿⇂ ↿⇂ ↿⇂
3p 3p 3p
↿⇂
Energy

3s
↿⇂ ↿⇂ ↿⇂ ↿ ↿ ↿ ↿⇂ ↿⇂ ↿
2p 2p 2p 2p 2p 2p 2p 2p 2p
↿⇂ ↿⇂ ↿⇂
2s 2s 2s

↿⇂ ↿⇂ ↿⇂
1s 1s 1s
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Development of the Periodic Table

However, Mendeleev could not explain inconsistencies such as argon coming before potassium in
the periodic table, despite having a higher atomic mass.

In 1913, Henry Moseley discovered the correlation between the number of protons (atomic
number) and frequency of X-rays generated. Ordering the periodic table by atomic number
instead of atomic mass enabled scientists to make sense of discrepancies. Entries today include
atomic number and symbol; and are arranged according to electron configuration.

Summarizes
• Atomic numbers.
• Atomic weights.
• Physical state (solid/liquid/gas).
• Type (metal/non-metal/metalloid).

Periodicity
• Elements with similar properties are arranged in vertical groups.
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Modern Periodic Table

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Classification of Elements
The main group elements (also called the representative elements) are the elements in
Groups 1A through 7A.
The noble gases are found in Group 8A and have filled p subshells.
The transition metals are found in Group 1B and 3B through 8B.
Group 2B have filled d subshells and are NOT transition metals.
The lanthanides and actinides make up the f-block transition elements.

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The Modern Periodic Table

There is a distinct pattern to the electron configurations of the elements in a particular
group.
For Group 1A: [noble gas]ns1 For Group 2A: [noble gas]ns2

Electron Configurations of Group 1A and Group 2A Elements

Group 1A Group 2A
Li [He]2s1 Be [He]2s2
Na [Ne]3s1 Mg [He]2s2
K [Ar]4s1 Ca [He]2s2
Rb [Kr]5s1 Sr [He]2s2
Cs [Xe]6s1 Ba [He]2s2
Fr [Rn]7s1 Ra [He]2s2

The outermost electrons of an atom are called the valence electrons.

Valence electrons are involved in the formation of chemical bonds.
Similarity of valence electron configurations help predict chemical properties.
All electrons associated with the highest principle quantum number are valence
For Group 1A: [noble gas]ns1 For Group 7A: [noble gas]ns2np5 46
core valence core valence

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Practice

Determine the number of valence electrons for the following elements:

K 1 valence e– Cu 1 valence e–

Mg 2 valence e– Mo 6 valence e–

Se 6 valence e– Ni 10 valence e–

I 7 valence e– Zn 2 valence e–

Al 3 valence e– Fe 8 valence e–

Si 4 valence e– Cr 6 valence e–

When the d shell is filled (d10), then the d electrons

don’t count as valence. 47

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Electron Configurations of Ions

To write the electron configuration of an ion formed by a main group element:
1. Write the configuration for the atom.
2. Add or remove the appropriate number of electrons. Positive ions, remove electrons;
negative ions, add electrons

10 electrons total,
Na: 1s22s22p63s1 Na+: 1s22s22p6
isoelectronic with Ne

– 18 electrons total,
Cl: 1s22s22p63s23p5 Cl : 1s22s22p63s23p6 isoelectronic with Ar

Species with identical electron configurations to the noble gas to the right are called
isoelectronic
Common monatomic ions arranged by their positions in the periodic table
Note that mercury(I) is a polyatomic ion ( Hg 2+
2 )

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Practice
Write electron configurations for the following ions of main group elements: (a) N 3–, (b) Ba2+,
and (c) Be2+. (a) [He]2s22p6
(b) [Kr]5s24d105p6
(c) 1s2
Determine the electron configuration for the following ions:

Cl– [Ar]3s23p6

N3– [He]2s22p6

K+ [Ne]3s23p6

Ca2+ [Ne]3s23p6
Are any of them isoelectronic?

Cl–, K+, Ca2+

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Electron Configurations of d-block Elements

Ions of d-block elements are formed by removing electrons first from the shell with the highest
value of n.
For Fe to form Fe2+, two electrons are lost from the 4s subshell not the 3d.
Fe: [Ar]4s23d 6 Fe2+: [Ar]3d 6
Fe can also form Fe3+, in which case the third electron is removed from the 3d subshell.
Fe: [Ar]4s23d 6 Fe3+: [Ar]3d 5

Write electron configurations for the following ions of d-block elements: (a) Zn2+, (b) Mn2+, and
(c) Cr3+.
(a) [Ar]3d10 (b) [Ar]3d5 (c) [Ar]3d3

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Practice
Determine the electron configuration for the following ions:

Fe+2 [Ar]3d6

Fe+3 [Ar]3d5

Cr+3 [Ar]3d3

Ti+2 [Ar]3d2

Ti+4 [Ne]3s23p6

Ni+2 [Ar]3d8

Ag+ [Kr]4d10
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Periodic Trends and Properties of Elements

Atomic radius is the distance between the nucleus of an atom and its valence shell.
(a) Atomic radius in metals, or metallic radius, is half the distance between the nuclei of
two adjacent, identical metal atoms.
(b) Atomic radius in nonmetals, or covalent radius, is half the distance between adjacent,
identical nuclei connected by a chemical bond.

Effective nuclear charge (Zeff ) is the actual magnitude of positive charge that is
“experienced” by an electron in the atom.
In a multi-electron atom, electrons are simultaneously attracted to the nucleus and repelled by
one another.
This results in shielding, where an electron is partially shielded from the positive charge of
the nucleus by the other electrons.
Although all electrons shield one another to some extent, the most effective are the core
electrons.
As a result, the value of Zeff increases steadily from left to right because the core electrons
remain the same but Z increases.
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Effective Nuclear Charge

Zeff increases steadily from left to right because the core electrons remain the same but Z
increases.

Li Be B C N O F
Z 3 4 5 6 7 8 9
Zeff 1.28 1.91 2.42 3.14 3.83 4.45 5.10

In general, the effective nuclear charge is given by: Zeff = Z – σ

Z is the nuclear charge, the number of protons in the nucleus.
σ is the shielding constant.

Zeff increases from left to right across a period; changes very little down a column.

Example of He:
Removal of 1st e– requires less
energy than removal of the
second e– due to shielding
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Atomic Radius

The atomic radius increases from top to bottom down a group.

Increasing n, so outermost shell lies farther from the nucleus

Atomic radius decreases from left to right across a period.

Increasing Zeff which draws the valence shell closer to the
nucleus

Atomic radius decreases left to right across a period due to increased electrostatic attraction
between the effective nuclear charge and the charge on the valence shell.

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Increasing
Practice ATOMIC RADIUS

Referring only to a periodic table, arrange the elements P, S, and

O in order of increasing atomic radius.
Cs
O<S<P

Using only the periodic table arrange the following elements in order of increasing atomic
radius: Astatine, Bromine, Chlorine, Fluorine, Iodine

F < Cl < Br < I < At

Which is the largest atom below?
A. O
B. N
C. Al
D. S
E. Mg
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Ionization Energy
Ionization energy (IE) is the minimum energy required to remove an electron from an atom
in the gas phase.
The result is an ion, a chemical species with a net charge.
Na(g) ⟶ Na+(g) + e−
Sodium has an ionization energy of 495.8 kJ/mol. Specifically, 495.8 kJ mol–1 is the first ionization
energy of sodium, IE1(Na), which corresponds to the removal of the most loosely held electron.

In general, as Zeff increases, ionization energy also increases. Thus, IE1 increases from left to right
across a period.

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Ionization Energy
Within a given shell, electrons with a higher value of
l are higher in energy and thus, easier to remove.

Removing a paired electron is easier because of the

repulsive forces between two electrons in the same
orbital.

It is possible to remove additional electrons in subsequent ionizations, giving IE1, IE2, and so on.
Na(g) ⟶ Na+(g) + e− Na+(g) ⟶ Na+2(g) + e−
IE1(Na) = 496 kJ/mol IE2(Na) = 4562 kJ/mol
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57

Increasing

Ionization Energy Ionization Energy

F
It takes more energy to remove the 2nd, 3rd, 4th, etc. electrons
because it is harder to remove an electron from a cation than an
atom.
It takes much more energy to remove core electrons than
valence.
Core electrons are closer to nucleus.
Core electrons experience greater Zeff because of fewer filled
shells shielding them from the nucleus.

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Practice
Would you expect Na or Mg to have the greater first ionization energy (IE1)? Which should have
the greater second ionization energy (IE2)?
IE1(Mg) > IE1(Na) because Mg is to the right of Na in the periodic table (i.e., Mg has the greater
Zeff, so it is more difficult to remove its electron).

IE2(Na) > IE2(Mg) because the second ionization of Mg removes a valence electron, whereas the
second ionization of Na removes a core electron.

Which atom below has the greatest ionization energy?

A. Li
B. Ne
C. Na
D. Kr

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Electron Affinity
Electron affinity (EA) is the energy released when
an atom in the gas phase accepts an electron.
Cl(g) + e− ⟶ Cl–(g)

Like ionization energy, electron affinity increases from left to right across a period as Zeff
increases.
Easier to add an electron as the positive charge of the nucleus increases.

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Electron Affinity
It is easier to add an electron to an s orbital than to add one to a p orbital with the same
principal quantum number.
Easier to add an e– Harder to add an e–
Energy

Energy
↿ np np np ↿⇂ np np np
ns ns
Group 1A Group 2A

Within a p subshell, it is easier to add an electron to an empty orbital than to add one to an
orbital that already contains an electron.
Group 4A Group 5A
Easier to add an e– Harder to add an e–

↿ ↿ ↿ ↿ ↿
Energy

Energy
↿⇂ np np np ↿⇂ np np np
ns ns
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Electron Affinity
More than one electron may be added to an atom.
Process Electron Affinity
O(g) + e– ⟶ O–(g) EA1=141 kJ mol–1
O–(g) + e– ⟶ O2–(g) EA2=–741 kJ mol–1

While many first electron affinities are positive, subsequent electron affinities are always
negative.
Considerable energy is required to overcome the repulsive forces between the electron and
the negatively charged ion.
Increasing
Electron Affinity
F

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Practice
For each pair of elements, indicate which one you would expect to have the greater first
electron affinity, EA1: (a) Al or Si, (b) Si or P.
EA1(Si) > EA1(Al) because Si is to the right of Al and therefore has a greater Zeff.

EA1(Si) > EA1(P) because although P is to the right of Si, adding an electron to a P atom
requires placing it in a partially occupied 3p orbital. The energy cost of pairing electrons
outweighs the energy advantage of adding an electron to an atom with a larger Zeff.

Which process illustrates electron affinity?

A. Li ⟶ Li+ + e–
B. O + e– ⟶ O –
C. O + O ⟶ O2
D. Na + Cl ⟶ Na+ + Cl–

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Ionic Radius
The ionic radius is the radius of a cation or an
anion.

When an atom loses an electron to become a

cation, its radius decreases due in part to a
reduction in electron-electron repulsions in the
valence shell.

A significant decrease in radius occurs when all

of an atom’s valence electrons are removed.

When an atom gains one or more electrons and

becomes an anion, its radius increases due to
increased electron-electron repulsions.

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Isoelectronic Series
An isoelectronic series is a series of two or more species that have identical electron
configurations, but different nuclear charges.

All Are
Isoelectronic
–
O2– : 1s22s22p6 F : 1s22s22p6 Ne: 1s22s22p6

Isoelectronic Ions O2– F– Na+ Mg2+

Ionic Radius (pm) 126 119 116 86
Number of Protons 8 9 11 12
Number of Electrons 10 10 10 10

Increasing nuclear charge

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decreasing size

65

Practice
Identify the isoelectronic series in the following group of species and arrange them in order of
increasing radius: K+, Ne, Ar, Kr, P3–, S2–, and Cl–.

K+, Ar, Cl–, S2–, P3–

Which of two species below are isoelectronic?

A. O2–, C4–
B. N2–, Cl–
C. Mg, Na
D. Li+, Be+

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Periodic Trends Review

ATOMIC RADIUS
INCREASING ELECTRON AFFINITY
IONIZATION ENERGY

Cs

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