Beirut Arab University

Faculty of Science
Chemistry Department

PRINCIPLES OF CHEMISTRY
(CHEM 241)

(Fall 2017-2018)
 Chapter 7

ATOMIC STRUCTURE
AND
PERIODICITY
7.1 Electromagnetic Radiation
Different Colored
Fireworks

Mixture of:

An oxidizer (oxidizing agent)

Potassium nitrate

And

A fuel (reducing agent)

Aluminum
 Electromagnetic Radiation

Questions to Consider
• Why do we get colors?
• Why do different chemicals give us
different colors?
 Electromagnetic Radiation
Radiation provides an important means of energy transfer

• One of the ways that energy travels

through space.

• Three characteristics:
 Wavelength and Amplitude
 Frequency
 Speed
 Electromagnetic Radiation
Characteristics
• Wavelength () : distance between two peaks
or troughs in a wave.

• Amplitude is the vertical distance from the

midline of a wave to the peak or trough.
 Electromagnetic Radiation
Characteristics
• Frequency () : number of waves (cycles) per
second that pass a given point in space
• Speed (c) : speed of light in vacuum (3.00×108 m/s)
Maxwell (1873), proposed that visible light
consists of electromagnetic waves.

Electromagnetic
radiation is the
emission and
transmission of
energy in the form of
electromagnetic
waves.

Speed of light (c) in vacuum = 3.00 x 108 m/s

All electromagnetic radiation

x=c
The range of frequencies and wavelengths of
electromagnetic radiation is called the
electromagnetic spectrum.
Classification of Electromagnetic Radiation
Classification of Electromagnetic Radiation
Classification of Electromagnetic Radiation
 Electromagnetic Radiation

• All waves have:

frequency and wavelength
• symbol:  (Greek letter “nu”)  (Greek “lambda”)
• units: “cycles per sec” = Hertz “distance” (nm)

All radiation:  x  = c

where c = velocity of light = 3.00 x 108 m/sec

Note: Long wavelength

 small frequency
Short wavelength
 high frequency increasing increasing
increasing
frequency wavelength
wavelength
What’s nature of light?
According to classical physics, it is a wave
because of the following properties.

• Reflection
• Refraction
• Diffraction
 A photon has a frequency of 6.0 x 104 Hz. Convert
this frequency into wavelength (nm). Does this frequency
fall in the visible region? or Is this AM or FM frequency?


x=c
 = c/ 
 = 3.00x108 m/s/6.0x104 Hz
 = 5.0 x 103 m
 = 5.0 x 1012 nm

Radio wave
7.2 The Nature of Matter

The Dual Nature of Matter:

Wave-Particle Duality: “Wavicle”

• Einstein: Light wave is Light Particle

(1905) (“Photon”)
E = hν = hc/ λ

• De Broglie: Electron (Particle) is Wave

(1923) λ = h/mu
 When copper is bombarded with high-energy
electrons, X rays are emitted. Calculate the energy
(in joules) associated with the photons if the
wavelength of the X rays is 0.154 nm.

E=hx
E=hxc/
E = 6.63 x 10-34 (J•s) x 3.00 x 10 8 (m/s) / 0.154 x 10-9 (m)
E = 1.29 x 10 -15 J/photon

= (1.29 x 10 -15 J/photon)(6.022 x 1023photon/mol)

= 7.77x108 J/mol = 7.77x105 kJ/mol = 777 MJ/mol

7.3 The Atomic Spectrum of Hydrogen
Line Emission Spectrum of H Atom. HOW are they generated?

• Continuous spectrum (when white light is

passed through a prism) – contains all the
wavelengths of visible light.
Line spectrum: each line corresponds to a discrete
wavelength
 Hydrogen emission spectrum
The Jigsaw puzzle of the H emission spectra was solved
by Balmer (1885) without knowing its implications

1/λ = 1.097x107 (1/22-1/n2) m-1

= 0.01097 (0.25-1/n2) nm-1

where n = 3, λ = 656 nm
4, λ = 486
5, λ = 434
6, λ = 410
7.4 The Bohr Model
• Electron in a hydrogen atom
moves around the nucleus only
in certain allowed circular
orbits.

• Bohr’s model gave hydrogen

atom energy levels consistent
with the hydrogen emission
spectrum.

• Ground state: lowest possible

energy state (n = 1)
The Bohr Model

1. e- can only have specific

(quantized) energy values
2. light is emitted as e- moves
from one energy level to a
lower energy level

1
En = -RH ( )
n2

n (principal quantum number) = 1,2,3,…

RH (Rydberg constant) = 2.18 x 10-18J
E = h
 Electronic Transitions in the Bohr
Model for the Hydrogen Atom

An Energy-Level Diagram for

Electronic Transitions

Ephoton = DE = Ef - Ei
ni = 3 ni = 3
1
Ef = -RH ( n2 )
f
1
nf = 2 Ei = -RH ( n2 )
i
1 1
DE = RH ( )
n2i n2f

nf = 1
 Calculate the wavelength (in nm) of a photon
emitted by a hydrogen atom when its electron
drops from the n = 5 state to the n = 3 state.

1 1
Ephoton = DE = RH(
n2i n2f )
Ephoton = 2.18 x 10-18 J x (1/25 - 1/9)
Ephoton = DE = -1.55 x 10-19 J
Ephoton = h x c / 
 = h x c / Ephoton
 = 6.63 x 10-34 (J•s) x 3.00 x 108 (m/s)/1.55 x 10-19J
 = 1280 nm Is this IR or UV?
 What is the de Broglie wavelength (in nm)
associated with a 2.5 g Ping-Pong ball
traveling at 15.6 m/s?

 = h/mu h in J•s m in kg u in (m/s)

 = 6.63 x 10-34 / (2.5 x 10-3 x 15.6)
 = 1.7 x 10-32 m = 1.7 x 10-23 nm
• Bohr’s model is incorrect. This model only
works for hydrogen.

• Electrons do not move around the nucleus in

circular orbits.
• Light has both wave & particle properties
• de Broglie (1924) proposed that all moving
objects have wave properties.
• For light: E = h = hc / 
• For particles: E = mc2 (Einstein)

Therefore, mc = h / 

and for particles

(mass)x(velocity) = h / 

 for particles is called the de Broglie wavelength

7.5 The Quantum Mechanical Model of the Atom

Physical Meaning of a Wave Function

• The square of the function indicates the probability of

finding an electron near a particular point in space.
 Probability distribution – intensity of color is used
to indicate the probability value near a given point
in space.
7.5 The Quantum Mechanical Model of the Atom

Probability Distribution for the 1s Wave Function

7.5 The Quantum Mechanical Model of the Atom

Radial Probability Distribution

7.5 The Quantum Mechanical Model of the Atom

Relative Orbital Size

• Difficult to define precisely.

• Orbital is a wave function.
• Picture an orbital as a three-dimensional electron
density map.
• Hydrogen 1s orbital:
 Radius of the sphere that encloses 90% of the total
electron probability.
7.6 Quantum Numbers

• Principal quantum number (n) – size and energy

of the orbital.

• Angular momentum quantum number (l) – shape

of atomic orbitals (sometimes called a subshell).

• Magnetic quantum number (ml) – orientation of

the orbital in space relative to the other orbitals in
the atom.
7.6 Quantum Numbers

Quantum Numbers for the First Four Levels of Orbitals in

the Hydrogen Atom
7.6 Quantum Numbers

Exercise
For principal quantum level n = 3,
determine the number of allowed subshells
(different values of l), and give the
designation of each.

# of allowed subshells = 3
l = 0, 3s
l = 1, 3p
l = 2, 3d
7.6 Quantum Numbers

Exercise

For l = 2, determine the magnetic quantum

numbers (ml) and the number of orbitals.

magnetic quantum numbers = –2, – 1, 0, 1, 2

number of orbitals = 5
7.7 Orbital Shapes and Energies

S Orbitals have spherical

Shapes with the nucleus

in the center

Two Representations of the

Hydrogen 1s, 2s, and 3s Orbitals
7.7 Orbital Shapes and Energies

All the p Orbitals have dumbbell shapes

Representations of All Three 2p Orbitals

7.7 Orbital Shapes and Energies

All the d Orbitals have dumbbell shapes

Representations of the 3d Orbitals

7.7 Orbital Shapes and Energies

All the f Orbitals have dumbbell shapes

Representation of the f Orbitals

7.8 Electron Spin and the Pauli Principle

Electron Spin
• Electron spin quantum number (ms) – can be +½ or -
½.

• Pauli exclusion principle - in a given atom no two

electrons can have the same set of four quantum
numbers.

• An orbital can hold only two electrons, and they must

have opposite spins.
7.9 Polyelectronic Atoms

• Atoms with more than one electron.

• Electron correlation problem:

 Since the electron pathways are unknown, the
electron repulsions cannot be calculated exactly.

• When electrons are placed in a particular quantum

level, they “prefer” the orbitals in the order s, p, d,
and then f.
7.9 Polyelectronic Atoms

Penetration Effect
• A 2s electron penetrates to the nucleus more than one
in the 2p orbital.

• This causes an electron in a 2s orbital to be attracted

to the nucleus more strongly than an electron in a 2p
orbital.

• Thus, the 2s orbital is lower in energy than the 2p

orbitals in a polyelectronic atom.
7.9 Polyelectronic Atoms

Penetration Effect
• A 2s electron penetrates to the nucleus more than one
in the 2p orbital.

• This causes an electron in a 2s orbital to be attracted

to the nucleus more strongly than an electron in a 2p
orbital.

• Thus, the 2s orbital is lower in energy than the 2p

orbitals in a polyelectronic atom.
 Energy of orbitals in a single electron atom
Energy only depends on principal quantum number n

n=3

n=2
1
En = -RH ( n2 )

n=1
Energy of orbitals in a multi-electron atom
Energy depends on n and l

n=3 l = 2

n=3 l = 1
n=3 l = 0

n=2 l = 1
n=2 l = 0

n=1 l = 0
“Fill up” electrons in lowest energy orbitals (Aufbau principle)

C 6 electrons
B 5 electrons B 1s22s22p1
Be 4 electrons Be 1s22s2
Li 3 electrons Li 1s22s1

He 2 electrons He 1s2
H 1 electron H 1s1
The most stable arrangement of electrons in
subshells is the one with the greatest number of
parallel spins (Hund’s rule).

C 1s22s22p2
N 1s22s22p3
O 1s22s22p4
F 1s22s22p5
Ne 1s22s22p6
Order of orbitals (filling) in multi-electron atom

1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s
Electron configuration is how the electrons are distributed
among the various atomic orbitals in an atom.

number of electrons
in the orbital or subshell
1s1
principal quantum angular momentum
number n quantum number l

Orbital diagram

H
1s1
What is the electron configuration of Mg?
Mg 12 electrons
1s < 2s < 2p < 3s < 3p < 4s
1s22s22p63s2 2 + 2 + 6 + 2 = 12 electrons
Abbreviated as [Ne]3s2 [Ne] 1s22s22p6

What are the possible quantum numbers for the last

(outermost) electron in Cl?
Cl 17 electrons 1s < 2s < 2p < 3s < 3p < 4s
1s22s22p63s23p5 2 + 2 + 6 + 2 + 5 = 17 electrons
Last electron added to 3p orbital

n=3 l=1 ml = -1, 0, or +1 ms = ½ or -½

Outermost subshell being filled with electrons
 Paramagnetic Diamagnetic
unpaired electrons all electrons paired

2p 2p
7.12 Periodic Trends in Atomic Properties

Periodic Trends
• Ionization Energy

• Electron Affinity

• Atomic Radius
 Ionization Energy
• Energy required to remove an electron from a gaseous
atom or ion.
 X(g) → X+(g) + e–

Mg → Mg+ + e– I1 = 735 kJ/mol (1st IE)

Mg+ → Mg2+ + e– I2 = 1445 kJ/mol (2nd IE)
Mg2+ → Mg3+ + e– I3 = 7730 kJ/mol *(3rd IE)

*Core electrons are bound much more tightly than

valence electrons.
 Ionization Energy
• In general, as we go across a period from left to right,
the first ionization energy increases.

• Why?
 Electrons added in the same principal quantum
level do not completely shield the increasing
nuclear charge caused by the added protons.

 Electrons in the same principal quantum level are

generally more strongly bound from left to right on
the periodic table.
 Ionization Energy

• In general, as we go down a group from top to

bottom, the first ionization energy decreases.

• Why?
 The electrons being removed are, on average,
farther from the nucleus.
The Values of First Ionization Energy for the Elements in the First Six
Periods
 Concept Check

Explain why the graph of ionization energy versus

atomic number (across a row) is not linear.
electron repulsions

Where are the exceptions?

some include from Be to B and N to O
 Concept Check

Which atom would require more energy to

remove an electron? Why?
Na Cl
 Concept Check

Which atom would require more energy to

remove an electron? Why?
Li Cs
 Concept Check

Which has the larger second ionization energy?

Why?
Lithium or Beryllium
Successive Ionization Energies (KJ per Mole) for the Elements in Period 3
 Electron Affinity
• Energy change associated with the addition of an
electron to a gaseous atom.
 X(g) + e– → X–(g)

• In general as we go across a period from left to right,

the electron affinities become more negative.

• In general electron affinity becomes more positive in

going down a group.
 Atomic Radius
• In general as we go across a period from left to right,
the atomic radius decreases.
 Effective nuclear charge increases, therefore the
valence electrons are drawn closer to the nucleus,
decreasing the size of the atom.

• In general atomic radius increases in going down a

group.
 Orbital sizes increase in successive principal
quantum levels.
Atomic Radii for Selected Atoms
 Concept Check

Which should be the larger atom? Why?

Na Cl
 Concept Check

Which should be the larger atom? Why?

Li Cs
 Exercise

Arrange the elements oxygen, fluorine, and

sulfur according to increasing:

 Ionization energy
S, O, F
 Atomic size
F, O, S
7.13 The Properties of a Group: The Alkali Metals

The Periodic Table – Final Thoughts

1. It is the number and type of valence electrons

that primarily determine an atom’s chemistry.
2. Electron configurations can be determined from
the organization of the periodic table.
3. Certain groups in the periodic table have special
names.
7.13 The Properties of a Group: The Alkali Metals

Special Names for Groups in the Periodic Table

7.13 The Properties of a Group: The Alkali Metals

The Periodic Table – Final Thoughts

4. Basic division of the elements is into metals and

nonmetals.
7.13 The Properties of a Group: The Alkali Metals

Metals Versus Nonmetals

7.13 The Properties of a Group: The Alkali Metals

The Alkali Metals

• Li, Na, K, Rb, Cs, and Fr
 Most chemically reactive of the metals
 React with nonmetals to form ionic solids
 Going down group:
 Ionization energy decreases
 Atomic radius increases
 Density increases
 Melting and boiling points smoothly decrease
 END
OF
CHAPTER 7