Chapter 7

Atomic Structure
Electronic Structure
Our goal:
• Understand why some substances behave as they do.
• For example: Why are K and Na reactive metals? Why do
H and Cl combine to make HCl? Why are some
compounds molecular rather than ionic?
Atom interact through their outer parts, their electrons.
The arrangement of electrons in atoms are referred to as their
electronic structure.
Electron structure relates to:
• Number of electrons an atom possess.
• Where they are located.
• What energies they possess.
 The Wave Nature of Light
Study of light emitted or absorbed by substances has lead to the
understanding of the electronic structure of atoms.
Light made up of electromagnetic (E.M) radiation
Characteristics of light:
• All waves have a characteristic wavelength, , and amplitude, A.
• The frequency, , of a wave is the number of cycles which pass a
point in one second. Measured in hertz , 1 hertz = 1
cycle/second
• The speed of a wave, v, is given by its frequency multiplied by
its wavelength: λ α (1/ ν) λ ν = constant (c)
c=λν c : speed of light = 3 x 108 m/s
Identifying  and 
Electromagnetic Radiation
• Modern atomic theory arose out of studies of the
interaction of radiation with matter.
• Electromagnetic (E.M.) radiation moves through a
vacuum with a speed of 2.99792458  108 m/s.
• There are many kind of E.M. radiation with different
wavelengths and frequencies shown in the following
figure.
• Visible radiation is the only part our eye can detect. It has
wavelengths between 400 nm (violet) and 750 nm (red).
The Electromagnetic Spectrum
Example(1):
What is the wavelength of light with a frequency 5.89 x 10 5
Hz.
c 3 x 10 8
m/s = 509 m
λ= ν = (Radio wave)
5.89 x 10 s
5 -1

Example (2):
What is the frequency of blue light with a wavelength of
484 nm?

c 3 x 108 m/s
ν= λ = = 6.2 x 10 s or Hz
14 -1
484 x 10 m
-9
The Nature of Matter
In 1990 Matter and energy were seen as different from each
other in fundamental ways
Matter:
• consist of particles
• Particles have a mass
• Its position in space can be specified.
Energy:
• could come in waves, with any frequency.
• Massless and delocalized.
• Their position in space could not be specified.
It was assumed that there was no intermingling of matter
and light
At the beginning of 20 century, certain experimental results
suggested that this picture was incorrect
The first important advance came from Max Planck, he found that
the cooling of hot objects couldn’t be explained by viewing
energy as a wave.
Plank found that the results could not be explain in term of the
physics of his day (matter absorb or emit any quantity of energy) .
Plank account for these observation by postulating that:
The energy can be gained or lost only in whole-number multiple
of the quantity hν
∆ E = nhν where n is an integer (1, 2, 3…).
h : is Planck’s constant = 6.626 x 10-34 J s
It seemed clear that energy is quantized and can occur in discrete
unit of size hν , these packets of energy (hν) are called quantum.
A system can transfer energy only in whole quanta.
Thus energy seems to have particulate properties
The next development came when Einstein proposed that E.M.
radiation is itself quantized.
He suggested that E.M. radiation can be viewed as a stream of
“particles” called photons
Each photon has energy Ephoton = hν = hc/λ
Combine this with E = mc2 (Einstein equation)
m = E /c2 m= hc/λ
c 2
you get the apparent mass of a photon
m = h / (λc)
Does a photon really have a mass? The answer appears to be yes.
However, it is clear that photons do not have mass in the classical
sense. A photon has mass only in relativistic sense – it has no rest
mass.
We can summarize the important conclusions from the work of
Plank and Einstien as follows:
 Energy is quantized, it can occur only in discrete unit called
quanta.
 E.M. radiation, which was previously thought to exhibit only
wave properties, seems to show certain characteristics of
particulate matter as well.
This phenomenon is referred to as the dual nature of light
Is the opposite is true? That is, does matter exhibit wave
properties.
de Brolie supplied the answer to this question.
m = h /(λc) for a particle with velocity v
m = h /(λv) λ = h/(mv)
This equation, called de Brolie equation, allow us to calculate the
wave lenghth of particle
Example:
The laser light of a CD is 7.80 x 102 m. calculate
A) What is the frequency of this light?
B) What is the energy of a photon of this light?
C)What is the apparent mass of a photon of this light?

A) ν = c/λ ν = 3 x 108(m/s)/ 7.80x102 m = 3.85 x 105s-1

B) Ephoton = hν
Ephoton = 6.626 x 10-34 J s x 3.85 x 105s-1
Ephoton = 2.55 x 10-28 J
C) m = h / (λc)
m = 6.626 x 10-34 J s /7.80x102 m x 3x108(m/s)
m = 2.83x10-45 Js2/m2 = 2.83x10-45(kg m2/s2) s2/m2
m = 2.83x10-45kg
Example:
What is the wavelength of an electron with a mass of
9.11 x 10-31 kg traveling at 1.0 x 107 m/s?
m = h / (λc)
λ = h /mc

λ= 6.626 x 10 -34
Js
= 7.2 x 10 -11
m
9.11 x 10 kg x 1.0 x 10 m/s
-31 7
 The atomic spectrum of hydrogen
Another important experiment was the study of the emission
light by excited H-atoms. When hydrogen gas receives high-
energy spark, H2 molecules absorb energy, some of H-H
bonds are broken. The resulting H-atoms are excited; that is
they contain excess energy which they release by emitting
light of various wavelength to produce what is called the
emission spectrum of H-atoms.
To understand the significance of H-emission spectrum, we
must describe the continuous spectrum that results when
white light is passed through a prism,
continuous spectrum
• Contain all the wavelength of visible (white) light.
• All the colors are possible.
• Like the rainbow.
When H-emission spectrum in visible region is passed
through prism, only a few lines can be seen, each
correspond to a discrete wavelength. The H-emission
spectrum is called line spectrum.
Continuous spectrum
Hydrogen spectrum
• Emission spectrum because these are the colors it gives off or emits
• Called a line spectrum.
• There are just a few discrete lines showing

434 nm 656 nm

410 nm 486 nm •Spectrum

What is the significance of line spectrum of hydrogen?
• It indicate only certain energies are allowed for the
hydrogen atom.
• Energy of electron H-is quantized
• Only certain energies are possible.
• Use E = h= hc / 
 Bohr Model
He developed the quantum model of the hydrogen atom.
• He proposed that the atom was like a solar system, the
electron in H-atom move around the nucleus only in certain
allowed circular orbit
• The electrons were attracted to the nucleus because of
opposite charges.
• Didn’t fall in to the nucleus because it was moving around
• He didn’t know why but only certain energies were
allowed.
• He called these allowed energies: energy levels.
• Putting energy into the atom moved the electron away
from the nucleus from ground state to excited state.
• When it returns to ground state it gives off light of a
certain energy
• The energy levels for H-atom are shown in the following
figure.
The Bohr Ring Atom
n=4
n=3
n=2
n=1
 The Bohr Model
• for each energy level the energy is:
E = -2.178 x 10-18 J (Z2 / n2 )
n: is the energy level
• Z: is the nuclear charge, which is +1 for hydrogen.
• n = 1 is called the ground state
• when the electron is removed from the atom, n = 
• When the electron moves from one energy level to
another.
• ∆E = Efinal - Einitial

• ∆E = -2.178 x 10-18 J Z2 (1/ nf2 - 1/ ni2)

Example:
Calculate the energy need to move an electron from its
ground state to the third energy level.
∆E = -2.178 x 10-18 J Z2 (1/ nf2 - 1/ ni2)
∆E = -2.178 x 10-18 J (+1)2 (1/9 – 1/1)
∆E = +1.936 x 10-18 J (+ mean energy absorbed)
Example:
Calculate the energy released when an electron moves from
n= 4 to n=2 in a hydrogen atom.
∆E = -2.178 x 10-18 J (+1)2 (1/4 – 1/16)
∆E = - 5.2125 x 10-19 J
Example:
Calculate the energy required to remove the electron from
hydrogen atom in its ground state.
∆E = -2.178 x 10-18 J (+1)2 (1/ – 1/1)
∆E = 2.178 x 10-18 J
Bohr model:
• Only works for hydrogen atoms and other monoelectronic
species.
• electrons don’t move in circles
• the quantization of energy is right, but not because they are
circling like planets.
The negative sign of the energy level :
• increase the energy of the electron when you make it further
to the nucleus.
• the maximum energy an electron can have is zero, at an
infinite distance (n =.
The Quantum Mechanical Model of the atom

A totally new approach was needed.

Three physicists were at the forefront of this effort:
Heisenberg, de Broglie, and Schrödinger. The approach
they developed known as wave mechanics or quantum
mechanics
• De Broglie said matter could be like a wave.
• Schrödinger proposed an equation that contains both
wave and particle terms.
• Much math, but what is important are the solutions.
• Solving the equation leads to wave functions.
• The wave function is a F(x, y, z) Actually F(r,θ,φ)
• Solutions to the equation are called orbitals ( not Bohr orbits).
• Each solution is tied to a certain energy level.
• The wave function gives the shape of the electronic
orbital.
• The square of the wave function, gives the probability of
finding the electron, that is, gives the electron density for
the atom.
• There is a limit to what we can know from Schrödinger
equation.
• We can’t know how the electron is moving or how it gets
from one energy level to another.
Electron Density Distribution

•Probability of finding an electron in a

hydrogen atom in its ground state.
Quantum Numbers
There are many solutions to Schrödinger’s equation
Each solution can be described with quantum numbers that
describe some aspect of the solution.
• Principal quantum number (n):
has an integral value: 1, 2, 3, ……, it is related to the size
and energy of an orbital.
As (n) increase:
 orbital become larger, electron spends more time farther
from the nucleus
 higher energy, because the electron is less tightly bound
to nucleus, energy is less negative.
• Angular momentum quantum number (ℓ):
 has integer values from 0 to n-1 for each value of n
 It is related to the shape of the orbital (as shown in the
following figures
 the value of (ℓ) for a particular orbital is commonly
assigned a letter: ℓ = 0 is called s , ℓ = 1 is called p
ℓ =2 is called d , ℓ =3 is called ƒ , ℓ =4 is called g
• Magnetic quantum number (m ℓ):
• integer values between - ℓ and + ℓ including zero.
• The value of mℓ is related to the orientation of the
orbital in space relative to the other orbitals in the atom.
 s-orbitals
All s-orbitals are spherical.

1s 2s 3s
 P orbitals
There are three p-orbitals px, py, and pz.
The three p-orbitals lie along the x-, y- and z- axes of a
Cartesian system.
The letters correspond to allowed values of mℓ of -1, 0,an +1.

Electron-distribution of a 2p orbital.
d-orbitals
f-orbitals
• Electron spin quantum number (m s):
the electron has a magnetic moment with two possible
when the atom placed in an external magnetic field
• Can have 2 values , either +1/2 or -1/2
For our purpose, the main significance of electron spin is
connected with the postulate of Pauli: in a given atom no
two electrons can have the same set of four quantum
numbers (n , ℓ, m ℓ, and ms ), this is called Pauli exclusion
principle. Since electrons in the same orbital have the same
value of n , ℓ, m ℓ , they must have different values of ms .
Then, since only two value of ms are allowed, an orbital can
hold only two electrons, and they must have opposite spin.
Quantum number for the first four level of orbitals in H-
atom:
n ℓ Orbital mℓ No. of
designation orbitals
1 0 1s 0 1
2 0 2s 0 1
1 2p 1+ ,0 ,1- 3
3 0 3s 0 1
1 3p 1+ ,0 ,1- 3
2 3d 2+,1+ ,0 ,1- ,2- 5
4 0 4s 0 1
1 4p 1+ ,0 ,1- 3
2 4d 2+,1+ ,0 ,1- ,2- 5
3 4f 3+ ,2+ ,1+ ,0 ,1- ,2-,3- 7
Example:
 For n = 4, what are the possible values of ℓ.
ℓ = 0→ n -1 , so ℓ = 0 → 4-1
ℓ = 0, 1, 2, 3
s, p, d, f
 For ℓ = 2. What are the possible values of mℓ
mℓ = - ℓ → +ℓ mℓ = -2 → +2
mℓ = -2, -1, 0, +1, +2
 How many possible values for ℓ and mℓ are there when
n=3
ℓ = 3-1 = 2 ℓ = 0, 1, 2
for ℓ = 0 mℓ = 0 , for ℓ = 1 mℓ = -1, 0, +1
for ℓ = 2 mℓ = -2, -1, 0, +1, +2
 7p 6d
7s 6p 5f
5d
6s 5p 4f
4d
5s
4p
Increasing energy

4s 3d
3p
3s
2p
2s
Orbitals and Their Energies

1s
 The Periodic Table
• Developed independently by German Julius Lothar
Meyer and Russian Dmitri Mendeleev (1870”s)
• Didn’t know much about atom.
• Put atoms in columns by similar properties.
• Predicted properties of missing elements.
Aufbau Principle and the periodic table
Our main assumption is that the atoms have the same type
of orbitals as have been described from the hydrogen atom.
As protons are added one by one to the nucleus to build up
the elements, electrons are similarly added to these H-like
orbitals. This is called aufbau principle
H has one electron, occupy the 1s orbital
The configuration for H can be represent as:
H: 1s1
Quantum no. for the electron is:
1s n=1, ℓ = 0, mℓ =0, ms =+1/2
Helium has two electron
Helium has two electrons
He: 1s2 Quantum no. for the first electron
is: n=1, ℓ = 0, mℓ =0, ms =+1/2
1s
Quantum no. for the second electron
is: n=1, ℓ = 0, mℓ =0, ms = -1/2
Lithium has three electrons
Li: 1s2 2s1 2p

1s 2s 2p
Be: 1s 2s 2p
2 2

1s 2s 2p
B: 1s 2s 2p
2 2 1

1s 2s 2p
 C: 1s2 2s2 2p2
1s 2s 2p
Two electrons occupy 2p orbital, since there are three 2p
orbitals with the same energy, the mutually repulsive
electrons will occupy separate 2p orbitals
Hund’s rule: the lowest energy configuration for an atom is
the one having the maximum number of unpaired electrons.

N: 1s2 2s2 2p3

1s 2s 2p
O: 1s2 2s2 2p4
1s 2s 2p
 F: 1s2 2s2 2p5
1s 2s 2p
Ne: 1s2 2s2 2p6
1s 2s 2p
With neon, the orbital with n =1 and n = 2 are now completely
filled.
Na: 1s2 2s2 2p63s1 can be abbreviate as Na : [Ne] 3s1

Ne
Write the symbol of the noble gas before the element
Then the rest of the electrons.
Mg: [Ne] 3s2
Al: [Ne] 3s2 3p1
At this point it is useful to introduce the following concepts:
• Valence electrons- the electrons in the outermost principle
quantum level of an atom (not d).
• Core electrons- the inner electrons
• Hund’s Rule- The lowest energy configuration for an atom is
the one have the maximum number of unpaired electrons in
the orbital.
Example:
element valence electrons core electrons
O 6 2
N 5 2
Ne 8 2
Mg 2 10
K: 1s2 2s2 2p63s13p64s1 or [Ar] 4s1 (valence electrons = 1)
Ca: 1s2 2s2 2p63s13p64s2 or [Ar] 4s2 (valence electrons = 1)
Sc: [Ar] 4s23d1 Ti: [Ar] 4s23d2 V: [Ar] 4s23d3
Valence electrons: 3 4 5
The expected configuration for chromium is:
Cr: [Ar] 4s23d4 however, the observed configuration is:
Cr: [Ar] 4s13d5 both 4s and 3d half-filled
Also the expected configuration for Cu is: Cu : [Ar] 4s23d9
The observed configuration is: Cu : [Ar] 4s 13d10
4s is half-filled, 3d is filled
Fill from the bottom up following the
arrows

7s 7p 7d 7f
6s 6p 6d 6f
5s 5p 5d 5f
4s 4p 4d 4f
3s 3p 3d
2s 2p
1s
Electron Configurations and the Periodic Table
The periodic table can be used as a guide for electron
configurations.
• the groups label (1A-8A) called the main-groups or
representative elements (no. of the group = valence electrons
• the groups label (1B-8B) called the Transion elements
• the (n+1)s orbital is always fill before nd orbitals.
• The period number is the value of n.
• Groups 1A and 2A (1 & 2) have the s-orbital filled.
• Groups 3A - 8A (13 - 18) have the p-orbital filled.
• Groups 3B - 2B (3 - 12) have the d-orbital filled.
• The lanthanides and actinides have the f-orbital filled.
• Elements in the same column have the same electron
configuration.
• Put in columns because of similar properties.
• Similar properties because of electron configuration.
• Noble gases have filled energy levels.
• Transition metals are filling the d orbitals
Periodic Trends in atomic properties
• Ionization energy (I.E.):
Ionization energy the energy required to remove an electron
form a gaseous atom or ion in its ground state.
X(g) → X+(g) + e
We will consider the energy required to remove several
electrons from Al in the ground state.
Al(g) → Al+(g) + e I1 = 580 kJ/mol
Al+(g) → Al+2(g) + e I2 = 1815 kJ/mol
Al+2(g) → Al+3(g) + e I3 = 2740 kJ/mol
Al+3(g) → Al+4(g) + e I4 = 11600 kJ/mol
Several points can be illustrated from these results:
Highest energy electron (the one bound least tightly) that is removed
first.
The first ionization energy I1 is the energy required to remove the first
electron (highest-energy electron)
 The value of I1 is considerably smaller than the value of I2 (second
ionization energy). The primary factor is simply charge, electron is removed
from +1 ion (Al+) .
The increase in positive charge bind the electron more firmly, and the
ionization energy increases. The same trend shows up in I3 and I4, where the
electron is removed from Al+2 and Al+3 ions respectively.
The increase in I.E. from I1 to I2 occur also because the first electron is
removed from 3p orbital that is higher in energy than 3s orbital from which
the second electron is removed.
The largest jump in I.E. by far occur in going from the I3 and I4 because
Al+3 has the configuration (1s2 2s2 2p6), the core electrons are bound much
more tightly than valence electrons.
In the following table, the ionization energies for all the period 3
are given. Note the large jump in energy in each case in going
from removal of valence electrons to removal of core electrons

Symbol I1 I2 I3
H 1312
He 2731 5247
Li 520 7297
Be 900 1757 11810
B 800 2430 14840
C 1086 2352 3569
N 1402 2857 4619
O 1314 3391 4577
F 1681 3375 5301
Ne 2080 3963 6045
 The values of the first I.E. for the elements
He are shown in the following figure:
First Ionization energy
N

H C
Be

B
Li

Atomic number
Note that:
 As you go down a group first I.E. decreases because of electron
being removed are, on average, farther from the nucleus. As n
increases, the size of the orbital increases, and the electron is easier to
remove.
 As you go across a period from left to right, first I.E. increases
because - Same shielding (same principle
quantum level) .
- Increasing nuclear charge (electrons are
strongly bound)
There are some trends in I.E. in going across period. For example,
trends occur from Be to B and from N to O. it can be explain in term
of electron repulsion. Half-filled and filled orbitals are harder to
remove electrons from

The ionization energies for the representative elements are
summarized in the following figure
• Atomic Size or radius:
The size of the orbital cannot be specified exactly (The electron cloud
doesn’t have a definite edge), neither can the size of an atom.
We can make some arbitrary choice to obtain values for atomic radii.
These values can be obtain by measuring the distance between atoms
in chemical compounds.
For example, in Br2 molecule, the distance between the two nuclei is
228 pm. The Br atomic radius is assumed to be half this distance, or
114 pm, as shown in the following figure.
Atomic Size

}
Radius
• Atomic Radius = half the distance between two nuclei
of a diatomic molecule
•Influenced by two factors
•Shielding
•More shielding is further away
•Charge on nucleus
•More charge pulls electrons in closer
As we go down a group each
atom has another energy level.
H
So the atoms get bigger Li
Na

Rb
• As you go across a period the radius gets smaller.
• Same energy level
• More nuclear charge
• Outermost electrons are closer

Na Mg Al Si P S Cl Ar
 Rb
K

Overall
Atomic Radius (nm)

Na

Li
Kr
Ar
Ne
H

10 Atomic Number
Electron Affinity:
The energy change associated with adding an electron to a
gaseous atom.
X(g) + e X-(g)
High electron affinity gives you energy-
• exothermic
• More negative
 In general, electron
affinity becomes more
exothermic as you go
from left to right across a
row.
Increase (more - ) from
left to right (greater
nuclear charge).
• Decrease as we go down
a group (More shielding)
Trends in Electron Affinity

There are again,

however, two
discontinuities in
this trend.

•© 2009, Prentice-Hall,
Trends in Electron Affinity

• The first occurs between

Groups IA and IIA.
• The added electron must
go in a p-orbital, not an s-
orbital.
• The electron is farther
from nucleus and feels
repulsion from the s-
electrons.

•© 2009, Prentice-Hall,
Trends in Electron Affinity

• The second occurs

between Groups IVA and
VA.
• Group VA has no empty
orbitals.
• The extra electron must
go into an already
occupied orbital, creating
repulsion.

•© 2009, Prentice-Hall,
Ionic Size
• Cations form by losing electrons
• Cations are smaller than the atom they come from
• Metals form cations
• Cations of representative elements have noble gas configuration.
Ionic size
• Anions form by gaining electrons
• Anions are bigger than the atom they come from
• Nonmetals form anions
• Anions of representative elements have noble gas configuration.
Configuration of Ions
• Ions always have noble gas configuration
• Na is 1s22s22p63s1

• Forms a 1+ ion - 1s22s22p6

• Same configuration as neon
• Metals form ions with the configuration of the noble gas before them
- they lose electrons
Configuration of Ions
• Non-metals form ions by gaining electrons to achieve noble gas
configuration.
• They end up with the configuration of the noble gas after them.
Group trends
• Adding energy level
• Ions get bigger as you go down
Li+1
Na+1
K+1
Rb+1

Cs+1
Periodic Trends
• Across the period nuclear charge increases so they get smaller.
• Energy level changes between anions and cations

N-3
B +3 O-2 F-1
Li+1

Be +2 C+4
Size of Isoelectronic ions
• Iso - same
• Iso electronic ions have the same # of electrons
• Al+3 Mg+2 Na+1 Ne F-1 O-2 and N-3
• all have 10 electrons
• all have the configuration 1s22s22p6
Size ofions
• Positive Isoelectronic ions
have more protons so they are smaller

N-3
O-2
Ne F-1
Al +3 Na+1

Mg+2
Electronegativity
Electronegativity
• The tendency for an atom to attract electrons to itself when it is
chemically combined with another element.
• How “greedy”
• Big electronegativity means it pulls the electron toward itself.
• Atoms with large negative electron affinity have larger
electronegativity.
Group Trend
• The further down a group more shielding
• Less attracted (Zeff)
• Low electronegativity.
Periodic Trend
• Metals are at the left end
• Low ionization energy- low effective nuclear charge
• Low electronegativity
• At the right end are the nonmetals
• More negative electron affinity
• High electronegativity
• Except noble gases
Ionization energy, electronegativity
Electron affinity INCREASE
Atomic size increases,

Ionic size increases

Parts of the Periodic Table
 The information it hides
• Know the special groups
• It is the number and type of valence electrons that determine an atom’s
chemistry.
• You can get the electron configuration from it.
• Metals lose electrons have the lowest IE
• Non metals- gain electrons most negative electron affinities
The Alkali Metals

• Doesn’t include hydrogen- it behaves as a non-metal

• decrease in IE
• increase in radius
• Decrease in density
• decrease in melting point
• Behave as reducing agents
Reducing ability

• Lower IE< better reducing agents

• Cs>Rb>K>Na>Li
• works for solids, but not in aqueous solutions.
• In solution Li>K>Na
• Why?
• It’s the water -there is an energy change associated with dissolving
Hydration Energy

• Li+(g) → Li+(aq) is exothermic

• for Li+ -510 kJ/mol

• for Na+ -402 kJ/mol

• for K+ -314 kJ/mol

• Li is so big because of it has a high charge density, a lot of charge on a
small atom.
• Li loses its electron more easily because of this in aqueous solutions
The reaction with water
• Na and K react explosively with water
• Li doesn’t.
• Even though the reaction of Li has a more negative H than that of Na
and K
• Na and K melt
• H does not tell you speed of reaction
• More in Chapter 12.