Atomic Structure

The Importance of Electromagnetic Radiation

• The interaction of electromagnetic waves or light with matter is a
powerful means to probe the structure of atoms and molecules.
• Electromagnetic Radiation carries energy through space
• All types of ‘ER’ travels at the speed of light (c = 3.0 x 10 8 m s-1)

• UV/Visible = electron location IR = detects different types of bonds

 The Wave Nature of Light
• All types of ‘ER’ have wavelike characteristics
– Wavelength ()
• Crest to crest; trough to trough
• Units: m, nm, Å (10-10)
– Frequency ()
• Number of complete waves passing
a point in a given amount of time
• Units: cycles/sec; s-1, Hertz (Hz)
–  and  have an inverse relationship
• c = 

1. Which wave has the higher frequency?

2. If one wave represents visible light and the other

represents infrared radiation, which is which?

3. If one wave represents blue light and the other red

light, which is which?
 Practice Problems
1. The yellow light given off by a sodium vapor lamp used for public
lighting has a wavelength of 589 nm. What is the frequency of this
radiation?

= c/ = (3.0 x 108 m s-1)/(589 x 10-9 m) = 5.09 x 1014 s-1

2. A laser used in eye surgery to fuse detached retinas produces radiation

with a wavelength of 640.0 nm. Calculate the frequency of this
radiation.

= c/ = (3.0 x 108 m s-1)/(640.0 x 10-9 m) = 4.688 x 1014 s-1

3. An FM radio station broadcasts

8 electromagnetic
1 radiation at a
c MHz.
frequency ofλ103.4 3.0x10 ms the wavelength of this radiation.
Calculate
   2.901m
ν 103.4x106 Hz
 Quantized Energy and Photons
The wave-particle “dual” nature of light!
Max Planck (1858-1947)
Emission of light from hot objects

• Energy can be either released or absorbed by atoms only in discrete

“chunks” of some minimum size.
• The smallest quantity of energy that can be emitted or absorbed as
‘ER’ is called QUANTUM (aka PHOTON)
– Energy of a single quantum is dependant on the frequency of the radiation
times a constant
• E = h
• h = Plank’s constant = 6.63 x 10-34 J-s
-1
 Quantized Energy and Photons
The wave-particle ‘dual’ nature of light!

Einstein(1879-1955)
Emission of electrons
from metal surfaces

Photoelectric effect supports the idea

that radiant energy is quantized.
•Energy travels in tiny packets
called PHOTONS
•Electrons will only become ‘excited’ and
removed from an atom if the photon has
a minimum frequency

•The number of electrons ‘excited’ is

dependent on the intensity of the light
not the frequency.
 Practice Problems
1. Calculate the energy of one photon of yellow light with a
wavelength of 589 nm.

If c= and E=h then E=hc/

(6.63 x 10-34 J-s)(3.0 x 108 m s-1)/(589 x 10-9 m)
E= 3.38 x 10-19 J

2. If one photon of radiant energy supplies 3.38 x 10-19 J, then one

mole of these photons will supply…

19 23
3.38x10 J 6.02x10 photons 1
 2.03x10 Jmol
5

1photon 1mol
 Practice Problems
3. A laser emits light with a frequency of 4.69 x 10 14 s-1. What is
the energy of one photon of the radiation from this laser?
E=h= 3.11 x 10-19 J

4. If the laser emits a pulse of energy containing 5.0 x 10 17

photons of this radiation, what is the total energy of that
pulse? 17 19
5.0x10 photons 3.11x10 J
 0.16J
1pulse 1photon
5. If the laser emits 1.3 x 10-2 J of energy during a pulse, how
many photons are emitted during the pulse?
1.3x10 2 J 1photon
19
 4.2x10 16
photons
1pulse 3.11x10 J
 Quantized Energy and Photons
The wave-particle ‘dual’ nature of light!

• Emission of light from electronically excited gas atoms

• Elements emit radiation in only specific wavelengths called a line spectrum
– Line spectrums act as a fingerprint for elements
Spectral Lines
 Energy Levels & the Bohr Model (Just
read slide)
Energy levels are the DISTANCE of the
electron from the nucleus.
• CLOSER = LOWER energy level
• FARTHER = HIGHER energy level
• n = energy level
 Drawing Bohr Models just read
Hydrogen
1 1e- 1
2 2
3 3
4 3 4
5 4 5
6 5 6
7 6 7

4
5
 Drawing Bohr Models just read
Nitrogen 5e-
1 2e- 1
2 2
3 3
4 3 4
5 4 5
6 5 6
7 6 7

4
5
 7e-
Bohr
Bromine
18e- Model just
8e- read
1 2e- 1
2 2
3 3
4 3 4
5 4 5
6 5 6
7 6 7

4
5
 Ground State vs Excited State Just
read this slide
• The “assigned” energy level of an electron
is its GROUND STATE
• Electrons can JUMP to an EXCITED
STATE by absorbing energy!
• Electrons can FALL BACK to the
GROUND STATE by releasing energy!
 Why do elements have a unique spectral line ‘fingerprint’?

Neils Bohr (1885-1962)

Spectral Lines of Hydrogen

• Electrons orbit the nucleus in

discrete ‘quantized’ energy levels

• Ground state = lowest energy state

• Excited state= higher energy state

• e- jump by absorbing photons

• e- fall by releasing photons

• ΔE=Ef - Ei=Ephoton

• Ephoton=h=hc/
 Neils Bohr (1885-1962)
Spectral Lines of Hydrogen

• When Bohr combined the energy of the photon equation with the
Rydberg spectral line equation he got…
 1 1 
ΔE  (2.18x10 18
J) 2  2 
 nf ni 

ni = initial energy levelnf = final energy level

• nf < ni the ΔE is a (-) number indicating that energy is released

Ex: n=4 to n=2 you get ΔE= - 4.08 x 10-19 J

• nf > ni the ΔE is a (+) number indicating that energy is absorbed

Ex: n=2 to n=4 you get ΔE= + 4.08 x 10-19 J
 Practice Problems
1. Calculate the energy required to excite the hydrogen atom from level n=1 to
level n=2. Calculate the wavelength of light that must be absorbed by a
hydrogen atom in its ground state to reach this excited state.

 1 1  18  1 1
ΔE  (2.18x10 18
 
J) 2  2   (2.18x10 J) 2  2 
 nf ni  2 1 

ΔE = 1.635 x 10-18 J
The + value of ΔE indicates that the system has gained energy!

λ = hc/E λ = (6.626 x 10-34 J-s)(3.0 x 108 m s-1)/(1.635 x 10-18 J)

λ = 1.21 x 10-7 m = 121.6 nm
 Can the electron move in a wave motion?
• Einstein tells us that energy and mass are related:
– Energy does have mass: E=mc2
– Mass does have energy: m=E/c2

A scientist name Louis De Broglie took the relationship between mass

and energy and postulated that matter, under certain
conditions, could act as a wave.
E hc h
m 2  2 
c λc λc
• De Broglie re-arranged this equation to solve for 

h h
λ λ That is velocity
mc mv
• De Broglie’s equation illustrates that any object that has momentum (mass x
velocity) would give rise to a characteristic “matter” wave.
 De Broglie’s Atomic Model
• De Broglie expanded on Bohr’s model by stating that
their could only be ‘orbits’ of certain sizes
– The orbits had to fit whole # multiples of the wavelength
– 1 , 2 , 3 … but not 2.5 

• This concept helped justify that energy levels are quantized!

 What is wrong with De Broglie’s Model?
• Waves extend into space, therefore its location is not precisely defined

– One would anticipate that it is impossible to determine exactly

where an electron is located at any specific time.

Heisenberg’s uncertainty principle:

• Due to the dual particle/wave nature of the electron it is impossible to
know precisely the momentum and the location of the electron.
– The uncertainty of hydrogen’s electron is 1 x 10-9 m

– Since the size of the hydrogen atom is only 1 x 10-10 m, we don’t

really know where the electron is 

Electrons do NOT move in circular ‘orbits’ around the nucleus…

• If they did e- would crash into the nucleus… Bohr ignored this fact 
 Schrodinger’s Quantum Atomic Model
(1887-1961)
• Performed advanced calculus equations that described the wave function,
, of an electron
• When the wave function is squared, 2, information about the electrons
location within an allowed energy level can be determined
• 2 provides the probable location (electron density)

• The density of the dots represents the probability

of finding the electron.
• The regions with a high density of dots corresponds
to relatively large values of 2 and are therefore
regions where there is a high probability of finding the electron.
• These wave functions are called “orbitals”
 Model just read slide • Schrodinger’s Quantum
mechanics of atom (current)

Don’t know exact location of where

electrons are. There is a high probability
Electrons orbit electrons are in an orbital. Orbitals are a
around the nucleus region of space where electrons are
most likely found. Electron found in
Incorrect model
energy levels at different distances away
from the nucleus. We describe electrons
using the 4 quantum models
 Orbitals & Quantum Numbers
• The 3 coordinates that come from Schrodingers wave equations
are now known as the 3 quantum numbers that describe the 3-
D nature of the orbital.
– n= energy level (distance from nucleus—size)
– ℓ=angular momentum (subshell/shape—s, p, d, f)
– mℓ= orientation in space (x, y, z axis)

• The 4th QN, ms, was added later to describe the spin of the
electron

• The combination of the 4 quantum numbers are unique for each

electron and describe the probable location of the electron
 1st Quantum # “Energy Level (n)”
• The periodic table can help us determine the main
energy levels (shells) for the electrons within an
atom…average distance from nucleus This is like
knowing the e- lives in CA
1 n=1 (2e- max) 1
2 n=2 (8e- max) 2
n=3 (18e- max)
3 3
n=4+ (32e- max)
4 3 4
5 4 5
6 5 6
7 6 7

4
 2nd Quantum # “Sublevel”
The energy levels can be divided into different
sublevels (shapes)! Ex: a state can be divided
into different Cities-we are in Harbor City!
s=sphere p=dumbbell d=clover f=complex
1s

2s

3s As the Energy Level ↑

The Size of the Shape gets
Bigger!
 2nd Quantum # “Sublevel”
just read slide
The periodic table tells us what shape
the electrons are moving in! Each
energy level has been divided into
different sublevels (shapes)!
 3rd Quantum # “3D Orbital”
The sublevels (shapes) can be divided
into different 3D-orbitals- orientation!
Just like a city has different streets… We live on Western Ave!
Orientation in 3D # Orbitals Max #
space e-
(x, y, z axis)
s 1 2
p 3 6
Each orbital can
d 5 10
hold 2e- max!
f 7 14
3rd Quantum # “3D Orbital”
just read this slide
All the orbitals overlap one another and
exist simultaneously within the atom!

n=1 n=2 n=3 n=4

 3rd Quantum # “3D Orbital”
just read this slide
The periodic table can help us determine the # of orbitals
in each sublevel… # Atoms ÷ 2
1 s=1 (2e- max) 1
p=3 (6e- max)
2 d=5 (10e- max) 2
3 f=7 (14e- max)c 3
4 3 4
5 4 5
6 5 6
7 6 7

4
5
 4th Quantum # “Electron Spin”
• Each orbital can hold a maximum of 2
electrons
– These electrons repel one another
– Maximize electron distance they spin
in opposite directions
 Let’s Summarize! Just read
Main Energy Level (n=1-n=7)
s p d f
1 3 5 7

• Now we know your whole address ☺

24300 Western Ave
Harbor City, CA 90710
• Are we guaranteed to find you here every time we look?
– Quantum #’s give us the electrons address… this is just a
“probable” location for the electron in the empty space!
 Quantum Numbers
Number Name Description Meaning Mathematics

n Principal QN Energy Level Shell n=1, 2, 3, …

Distance from n= 1, 2, 3, …
Nucleus (size)

ℓ Angular Momentum General Shape Subshell s=0 d=2

QN ℓ= s, p, d, f p=1 f=3

mℓ Magnetic QN 3-D # of orbitals # of orbitals

Orientation in s=1, p=3, d=5, f=7 mℓ = 2ℓ + 1
Space (axis)
Ranges From
From -ℓ to +ℓ

ms Magnetic Spin QN Direction of Up spin ms = +1/2

Spin of e- Down spin ms = -1/2
Periodic Table & Quantum Numbers!
 Relationship Among Quantum Numbers
n Values of ℓ Subshells Values of mℓ # of Orbitals Total # of Orbitals
in subshell in Shell
1 0 1s 0 1 1

2 0 2s 0 1 4
1 2p 1, 0, -1 3
3 0 3s 0 1 9
1 3p 1, 0, -1 3
2 3d 2, 1, 0, -1, -2 5
4 0 4s 0 1 16
1 4p 1, 0, -1 3
2 4d 2, 1, 0, -1, -2 5
3 4f 3, 2, 1, 0, -1, -2, -3 7

• The collection of orbitals with the same value of n is called an electron shell.
– The total number of orbitals in a shell is n2

• The set of orbitals that have the same n and ℓ values is called a sublevel.

• Each orbital can hold a maximum of 2 electrons

 Practice Problems
1. For n=5 and ℓ=1
a. What is the designation for this subshell? 5p
b. How many orbitals are in this subshell? 3
c. Indicates the values for mℓ for each of these orbitals -1, 0, 1

2. For n=3 and ℓ=2

a. What is the designation for this subshell? 3d
b. How many orbitals are in this subshell? 5
c. Indicates the values for mℓ for each of these orbitals

-2, -1, 0, 1, 2
 Practice Problems
3. How many orbitals (different mℓ orbitals) are in the 4s subshell?
1
4. Identify all possible quantum number values for the 4s orbital:

4
n=_____ 0
ℓ=_____ 0
mℓ =_____ ms = +1/2
_____ or -1/2
5. How many orbitals (different mℓ orbitals) are in the 5p subshell?
3
6. Identify the quantum number values for the 5p orbitals in the space below:

5
n=_____ 1
ℓ=_____ m-1
ℓ =_____
+1/2
m or -1/2
s = _____

0
m =_____ +1/2
m = or
_____ -1/2
ℓ s

m1
=_____ +1/2
m or
= _____ -1/2
Helpful
Tools
 Writing Complete Electron Configurations!
• The electrons address is called its “electron configuration”
– COMPLETE electron configurations give a “partial”
address for EVERY electron in the atom!
1 # of e- in Sublevel 1
2
H = 1s 1
2
3 s Energy Level Sublevel-shape 3
4 3 4 p
5 4 5
6 5 d 6
7 6 7

4
5
f
 Writing Complete Electron
Configurations!
He = 1s 2 # of e- in Sublevel

1 Sublevel-shape 1
2
2
3
s Energy Level
3
4 3 4 p
5 4 5
6 5 d 6
7 6 7

4
5
f
 Writing Complete Electron Configurations!

O = 1s 2s 2p 2 2 4
2 e- in the 1st energy level in a
spherical shape
1 6 e- in the 2nd energy level 1
2 (2 e- spherical & 4 e- dumbbell shape) 2
3
3
4 s 3 4
p
5 4 5
6 5 d 6
7 6 7

4
5
f
 Writing Complete Electron
Configurations!
Fe = 1s2 2s22p6 3s2 3p6 4s2 3d6
1 1
2 2
3 3
4 3 4 p
5 4 5
6 s 5 d 6
7 6 7

4
5
f
 Short Hand “Noble Gas” Configurations
• The core electrons can be represented by placing the symbol
for the previous noble gas in [brackets].
1. Find your element… go backwards until you find a noble
gas!
2. Place the noble gas symbol in brackets… finish the e-
config.

1
S=[Ne]3s 3p 2 4
1
2 Stands for [1s22s22p6] 2
3 3
4 3 4
5 4 5
6 5 6
7 6 7
• The core electrons can be represented by placing the symbol
for the previous noble gas in [brackets].
1. Find your element… go backwards until you find a noble
gas!
2. Place the noble gas symbol in brackets… finish the e-
config.

Ga=[Ar]4s 3d 4p 2 10 1

1 Stands for 1
2 [1s22s22p63s23p6] 2
3 3
4 3 4
5 4 5
6 5 6
7 6 7
 Identifying Valence Electrons!
• Noble gas configuration makes it easy to identify the valence e-
• Always any INCOMPLETE sublevels
• Always ALL the e- in HIGHEST energy level (even if they are
full)

S=[Ne]3s 3p 2 4 6 Valence e-

Ful
Ga=[Ar]4s 3d 4p 2 l 10 1 3 Valence e-

Ful
W=[Xe]6s 5d 4f 5d 2 1 l 14 3
6 Valence e-
Not Full
 Practice Problems
7. Write the complete electron configuration for calcium, Ca. List the 4
quantum numbers for calcium’s last electron.

Calcium = 1s2 2s2 2p6 3s2 3p6 4s2

n= 4 ℓ=0 m ℓ= 0 ms= -1/2

8. Write the noble gas configuration for bromine, Br. List the 4
quantum numbers for bromine’s 27th electron.

Bromine = [Ar] 4s2 3d10 4p5

n= 3 ℓ=2 mℓ= -1 ms= -1/2

 Orbital Box Diagrams
• Sublevels are divided into orbitals
• Orbitals hold a maximum of 2 electrons each!
Sublevel # of Orbitals Total # of Electrons
s
1 2
p
3 6
d
5 10
f
7 14
• Boxes will be used to represent EACH orbital
• ↑↓ will be used to represent the electrons inside the orbitals
 Orbital Box Diagrams
• Each orbital is represented by using boxes.

↑↓ s
↑↓ ↑↓ ↑↓ p
↑↓ ↑↓ ↑↓ ↑↓ ↑↓ d
↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ f
• Orbital boxes are grouped together to represent their sublevels.
• The ↑ and ↓ show that electrons are spinning in opposite
directions!
 Orbital Box Diagrams
First start by writing the e- configuration!
Then draw the orbital box diagram!
Add the electron arrows in each orbital!

Oxygen = 1s 2s 2p 2 2 4

↑↓ ↑↓ ↑↓ ↑ ↑
1s 2 2s 2
2p 4
This gives us a complete description of the electrons
address!!!
Now we have the best chance of finding the e- in the empty
space!
 Orbital Box Diagrams
Silicon = 1s22s22p63s23p2
↑↓ ↑↓ ↑↓ ↑↓ ↑↓
1s2 2s2 2p6
↑↓ ↑ ↑
3s2 3p2
 Orbital Box Diagrams
Write the noble gas configuration for

Iodine= [Kr] 5s24d105p5

Draw the orbital box diagram for the valence e-
only
↑↓ ↑↓ ↑↓ ↑
5s2 5p5
 Practice Problem
Complete the following:
1. Complete electron configuration for titanium
1s2 2s2 2p6 3s2 3p6 4s2 3d2
2. Noble gas configuration for barium
[Xe] 6s2
3. Orbital box diagram for phosphorus
 Rules for Electron Placement within an Orbital

1. Aufbau:
lowest Energy Level fills first

2. Hund’s Rule:
1 e- per orbital (same spin)
before you pair e-
*within sublevel*

3. Pauli Exculsion Principle:

When e- are paired they
must have opposite spin
 Orbitals
• In order for electrons to occupy the lowest
energy state possible they must deal with:
• Attraction of electrons to protons
• Repulsion of electrons to electrons
• Particle-wave nature of e-

Coulombs law

• Quantum Number describe e- location!

 Electron Behavior

Paramagnetic: unpaired electrons; attracted by magnet

Diamagnetic: all electrons paired; repelled by magnet
 Electron Behavior
• The following electron configurations represent excited states.
Based on the Aufbau principal, write the ground state electron
configuration and identify the element.

1. 1s22s22p23s1
Ground state 1s22s22p3= nitrogen

2. 1s22s22p63p1
Ground state 1s22s22p63s1= sodium
  Exceptions to the Rule 

• The following represent the ground state electron configurations for

chromium and copper. Explain why these exceptions exist.

Cr: [Ar]4s13d5 _ _____

4s 3d
• When electrons spin in the same direction they have less energy and
are more stable.

Cu: [Ar]4s13d10 _ 

4s 3d
• When the d subshell is full the atoms lower energy levels are
complete and the atom is more stable.
 Periodic Trends

• Elements are arranged in order of increasing atomic number

• Columns (families) are groupings of elements that have similar
chemical properties.
• Some chemical properties exhibit patterns on the periodic table that
follow a distinct trend.
• Chemical properties depend on the electron arrangement within the
atom and the effective nuclear charge of the protons.
Effective Nuclear Charge (Zeff)
• The force of attraction
between an electron & nucleus
– Based on the strength of p+
– Based on e- repulsion
• Zeff < nuclear charge

– Zeff accounts for e- shielding

(screening) of core e- which
reduce the attraction to p+
Zeff = Z – S
– Z = # protons
– S = # core electrons
 The force of attraction increases as the nuclear charge increases
 The force of attraction decreases as the electron moves farther away
from the nucleus
 Trend in Effective Nuclear Charge

Explain why Zeff is stronger at the top of a column.

Explain why Zeff is stronger to the right of a row.
Explaining the Trend in Zeff
Across Row
# electrons shells are
the same
# protons increases

Down Column
# e- shells 
e- shielding 
 Trend in Atomic Radius
The atomic radius measures the size of a
neutral atom from the center of the
NUCLEUS to the outermost VALENCE
ELECTRON
 Explain the Trend in Atomic Radius
– DECREASES Across the Period (Left to Right)
• The atomic radius decreases. There is an increase in number of
p+, while the e- shells and e- shielding remains constant. The
e- are more attracted to p+ and are drawn in closer.

– INCREASES Down a Group (Top to Bottom)

• The atomic radius increase. There is an increase in the number
of energy levels and an increase in e- shielding and e- repulsion
of the core e-. The valence e- are less attracted to the nucleus
because it is difficult for them to feel the pull of p+.
Coulombic attraction depends on… just read slide

amount of charge distance between charges

2+ 2– 2+ 2–

1+ 1– 2+ 2–

As we go , more
coulombic attraction, no new
+ –
energy level, more pull,
smaller size

–
H + + –

He + + – –
 Practice Problems
• Referring to a periodic table, arrange the following atoms in
order of increasing size: 15P, 16S, 33As, 34Se

– Increasing means smallest to biggest 

– S<P<Se<As

• Arrange the following atoms in order of increasing atomic

radius: 11Na, 4Be, 12Mg

– Increasing means smallest to biggest 

– Be<Mg<Na
 Ionic Radius
Comparison of size between ion and neutral atom
Cations (+ ions)
• How do cations differ from there neutral atoms?
–Same # of protons
–less electrons

• Do cations have a stronger or weaker Zeff?

–Stronger
–decrease in electron-electron repulsion

• Are cations smaller or bigger (than neutral atoms)

–SMALLER… Zeff pulls e- in closer
–Most dramatic size change when last valence e-
is removed from the energy level.
 Ionic Radius
Comparison of size between ion and neutral atom
Anions (- ions)
• How do anions differ from there neutral atoms?
–Same # of protons
–more electrons

• Do anions have a stronger or weaker Zeff?

–Weaker
–increase in electron-electron repulsion

• Are anions smaller or bigger (than neutral atoms)

–BIGGER… Zeff causes e- to spread out farther
from the nucleus
 Trend in Ionic Radius
Increases Down a Column
 # e- shells/e- repulsion
The following ions are considered ISOELECTRONIC.
Compare & Contrast these ions.

ISOELECTRONIC Ions
Same # e-
Different # p+
Trend in Ionic Size for ISOELECTRONIC Ions

 # p+  ion size
• e- shielding & e- repulsion remains the same
•  p+ makes Zeff STRONGER & pulls e- in closer
 Practice Problems
1. Arrange these atoms and ions in order of decreasing size:
Mg2+, Ca2+, and Ca

Ca > Ca+2 > Mg+2

2. Which of the following atoms and ions is largest: S2-, S, O2-?

S-2
3. Arrange the ions K+, Cl-, Ca2+, and S2- in order of decreasing size
S-2 > Cl-1 > K+1 > Ca+2
Isoelectronic = 18 electrons

4. Which of the following ions is largest, Rb+, Sr2+, or Y3+?

Rb+
 Ionization Energy
• The minimum energy required to remove an e- from the ground
state of an isolated atom or ion in its gas phase.
– Energy absorbed to become a + ion

What is the trend in I.E.?

Do you notice anything strange?
 Trend in Ionization Energy
DECREASES Down the Column
1. The # of electron shells increases
• e- shielding & e- repulsion
•  Zeff = easier to remove the e-
2.  energy levels
• e- start with more energy
• Less energy needed to leave
 Trend in Ionization Energy
INCREASES Across the Row (Left to Right)
• Same # of electron shells &  # protons
–  Zeff = harder to remove the e-

Exceptions to the IE Trend:

• Be requires more IE than B

• Electrons in the p subshell start with

more energy than s subshell electrons
– That is why we fill the p subshell after
thes subshell!
– Less energy needs to be absorbed to
remove the p subshell electrons
 Trend in Ionization Energy
INCREASES Across the Row (Left to Right)
• Same # of electron shells &  # protons
–  Zeff = harder to remove the e-
Exceptions to the IE Trend:
• O requires less IE than N

Nitrogen

Oxygen
e- repulsion Zeff
& makes it easier to
remove oxygen e-
 I. E. Metals vs. Non-Metals

• Metals have low I.E. & lose e- easily (+ ions)

• Non-Metals have high I.E. & don’t lose electrons
 Practice Problems
1. Referring to a periodic table, arrange the following atoms
in order of increasing first IE: Ne, Na, P, Ar, K
K < Na < P < Ar < Ne

2. Which has the lowest first IE, B, Al, C, or Si? Which has the
highest first IE?
Lowest = Al Highest = C
3. Predict whether sulfur would have a higher or lower IE
than phosphorus. Explain your answer.

P= S=

Lower: due to  e- repulsion

 Removing Successive Electrons
• First IE… removing the 1st electron
Al  Al+1 + 1e-

• Second IE… removing the 2nd electron Always remove

Al+1  Al+2 + 1e- 1 e- at a time

• Third IE… removing the 3rd electron

Al+2  Al+3 + 1e-

• 1st IE < 2nd IE < 3rd IE < etc

– As electrons are removed Zeff increases in strength
• Same # protons acting on less electrons

• Core e- always requires more energy than valence e- to remove

 Practice Problems

1. Based on their locations on the periodic table, predict

which element will have the largest 2nd IE: Na, Ca, S
Na > S > Ca
2. Which will have a higher 3rd IE: Ca or S?
Ca > S
 Photoelectron Spectroscopy (PES)
• High energy UV or X-ray photons are used to excite e- in an atom
– Photon Energy > Ionization Energy of the atom
– Any electron can be ionized (valence and core) and the energy of
all electrons in the atom can be measured!
 PES Activity
• Do all electrons in an energy level have the same amount of energy?

Let’s take a look at some PES data:

www.chem.arizona.edu/chemt/Flash/photoelectron.html.
Relative # e-

Relative # e-

0 0
Energy Energy
 Electron Affinity
• A measure (based on energy released) of attraction of an
isolated atom (in its gaseous phase) when gaining an electron.
– Energy released to become a (-) ion

Atoms with a low Zeff will have a low EA

• Weak nucleus will struggle attracting e-
• Metals have a lower EA than non-metals

Atoms with a high Zeff will have a high EA

• Strong nucleus is good at attracting e-
• Non-metals have a higher EA than metals
 Trend in Electron Affinity
Across the Period (Left to Right)
• EA  due to the  # protons (↑ Zeff)
• Exceptions to the trend:
– Group 2
– Group 15
– Group 18

Down a Group (Top to Bottom)

• EA  due to  # e- shells (↓ Zeff)
• Exceptions to the trend:
– Oxygen & Fluorine
 Electron Affinity kJ/mol

Lower EA is due
Drop intoEAO & F being
Slightly (-) value so small
(across the row) they don’t
Indicates it is Have
Due to __ __ a__
lot of room
Possible to gain e- for another e-
e- arrangement.
EA > 0 means
The atoms do NOT
These elements
want another e-
Do NOT gain e-
 Practice Problems
1. The electron affinity of lithium is a negative value, whereas the
electron affinity of beryllium is a positive value. Use electron
configurations to account for this observation.
Li = 1s22s1 Li-1 = 1s22s2
Be = 1s22s2 Be-1 = 1s22s22p1

• When Be gains an electron it requires the addition of the 2p subshell

2. While the electron affinity of bromine is a negative quantity, it is

positive for Kr. Use electron configurations of the two elements to
explain the difference.
Br = [Ar]4s23d104p5 Br-1 = [Ar]4s23d104p6
Kr = [Ar]4s23d104p6 Kr-1 = [Ar]4s23d104p65s1

• When Kr gains an electron it requires the addition of the 5s subshell

 Electronegativity
• The ability of an atom, in a molecule, to attract electrons to itself.
– Scale of 1-4 that measures the strength of an atom in a bond.

Low Zeff will have a low EN

• Weak nucleus struggles to attract e-
• Metals have a lower EN

High Zeff will have a high EN

• Strong nucleus is good at attracting e-
• Non-metals have a higher EN
Trend in Electronegativity
F

Cl
Br
I
At

Li Na K Rb Cs
 Trend in Electronegativity
• INCREASES Across the Period (Left to Right)
– Increased # protons (↑ Zeff)

• DECREASES Down a Group (Top to Bottom)

– Increased # of e- shells (↓ Zeff)

• Sometimes EN values stay the same due to similar bonding

characteristics within a family of elements
• NOBLE GASES = 0 (UNREACTIVE)

• F = 4.0 (highest) Fr = 0.7 (lowest)

• EN values tend to radiate from fluorine
 Practice Problems
1. Arrange the following atoms in order of increasing
electronegativity values: F, Ba, S, Na, B
– Ba < Na < B < S < F

2. Explain how the trend in electronegativity relates to the

trend in ionization energy and the trend in electron
affinity.
– High Zeff means the nucleus is strong and good at
holding onto it’s own e- (high IE) and good at attracting
e- from other atoms (high EA).
– When an atom has a strong nucleus, high Zeff, it will
also be good at dominating the e- within a molecule
Periodic Trends
 Practice Problems
4. Draw the orbital box diagram for silicon, Si. List the 4 quantum
numbers for silicon’s valence electrons.

Electron n ℓ mℓ ms
11 3 0 0 +1/2
12 3 0 0 -1/2
13 3 1 -1 +1/2
14 3 1 0 +1/2