GENERAL CHEMISTRY

Principles and Modern Applications TENTH EDITION

PETRUCCI HERRING MADURA BISSONNETTE

Electrons in Atoms Chapter 8

8-1 Electromagnetic Radiation

•Light has wavelike

properties.

•Electric and magnetic

fields propagate as waves
through empty space or
through a medium.

•A wave transmits energy.

FIGURE 8-1
The simplest wave motion – traveling wave in a rope
Low 

High 

FIGURE 8-2
Electromagnetic waves
Frequency, Wavelength and Speed of
Electromagnetic Radiation

Frequency () in Hertz—Hz or s-1.

Wavelength (λ) in meters—m.
cm m nm Å pm
(10-2 m) (10-6 m) (10-9 m) (10-10 m) (10-12 m)

Velocity (c)—2.997925  108 m s-1.

c = λ λ = c/  = c/λ
 FIGURE 8-3
The electromagnetic spectrum
Clicker Question

Based on the
diagram and the
equation below
which of the
following
statements is true?
c = 
A. The frequencies of radio waves are greater than the frequencies of
visible waves.
B. The frequencies of ultraviolet waves are greater than the
frequencies of infrared waves.
C. The frequencies of gamma waves are smaller than the frequencies
of X-ray waves.
D. None of the above statements are true.
Light, electromagnetic radiation, has important wave characteristics

FIGURE 8-5
Interference in two overlapping light waves
The Photoelectric Effect
In the early 1900’s, experiments demonstrated that light also had
particle like qualities.

Heinrich Hertz, 1888

Light striking the surface of
certain metals causes
ejection of electrons.
 > o
threshold frequency

#e-  I
ek  
Albert Einstein 1905
The Photoelectric
Effect

(b)

0 is the threshold
Ek frequency

(c)

b) Number of electrons emitted depends on the intensity of light but,

c) The kinetic energies of the emitted electrons depend on the frequency of the
light
For electron emission to occur, energy of light has to overcome the
binding energy (BE) of the electron to the metal surface.
Photoelectric effect
Light can also be thought of as a packet of energy, a photon.

Energy of a photon:
E=h
h = “Planck’s Constant” = 6.626 x 10–34 J s

Since  = c/, the energy of a photon is also:

E = hc/

Light has both wave and particle characteristics

Wave-particle duality
Clicker Question
To the right is a schematic
of the apparatus used for
photoelectric effect
measurements where 0 is
called the threshold
frequency. True or false, if
light of a higher frequency
is shone on the metal a
larger current will be
measured?

1. True
2. False
Photoelectric Effect Problem
Light with  = 1.3 x 1015 s–1 ejects electrons from cesium metal. If the
kinetic energy of the electrons is 5.2 x 10–19 J, what is the binding energy
of electrons in cesium metal?
E photon = h
= (6.626x10-34 Js)(1.3x1015 s -1 )
= 8.6x10-19 J

Conservation of Energy!
Ephoton = BE + KE so BE = Ephoton – KE

BE = (8.6 x 10–19 J) – (5.2 x 10–19 J) = 3.4 x 10–19J

PE Problem
Suppose that when a photoelectric effect experiment was carried out
using light with  = 7.50 x 1014 s-1, ejected electrons were detected with
a kinetic energy of 2.50 x 10-11 J. The experiment was then repeated
using light with  = 1.00 x 1015 s-1 and the same metal target, and
electrons were ejected with kinetic energy of 5.00 x 10-11 J. Use these
data to find a value for Planck's constant. (These are made up data so
the value for h will not be the real value).
 Ep = BE + KE

So, from 1st experiment: h1 = BE + KE1

And from 2nd experiment: hv2 = BE + KE2

Since metal is the same, BE is the same.

Subtracting:
h(1-2) = KE1-KE2

1 = 7.5x1014 s-1, KE1 = 2.50x10-11J and

2 = 1x1015 s-1, KE2 = 5x10-11J. Plug and chug.

h = 1 x 10-25 J.s
Atomic
Spectra
• Excited atoms emit light (neon signs, etc.)
• Emissions from different elements are different in
color.
 FIGURE 8-9
The atomic, or line, spectrum of helium
Existence of spectral lines is evidence of “quantized energy levels.”
Atomic Spectra: Emission

Excited Atom  De-excited Atom + Photon

E(atom) 
+ h
E(atom) = E(photon) = h
Atomic Spectra: Absorption

Atom + Photon  Excited Atom

E(atom)
+ h 

E(atom) = E(photon) = h
Problem - Energy
Levels
A hypothetical atom has only 4 energy levels. Emission spectrum
shows 6 lines at wavelengths of 100, 120, 150, 300, 500, and 750 nm.
Atomic energy levels usually get closer together as energy increases.

•Draw an energy level diagram for this atom

•Label the states by energies: E1 < E2 < E3 < E4
•Use arrows to show the 6 transitions, and assign the correct wavelengths
•Try to draw “to scale”
Six energy transitions

E4
E3

E2

E1
Energy calculation
100, 120, 150, 300, 500, and 750 nm

hc
E = h =

(6.626 x 10-34 J s)(3 x 108 m / s)
=
100 x 10-9 m
= 1.99 x 10-18 J

100 nm: 1.99x10–18 J

120 nm: 1.66x10–18 J
150 nm: 1.33x10–18 J
300 nm: 6.63x10–19 J
500 nm: 3.98x10–19 J
750 nm: 2.65x10–19 J
Clicker Question

The lowest frequency of emitted

light is associated with which
transition?

A. i
B. ii
C. iii
D. iv
E. Not enough information
Spectra and
Analysis

• Spectra exist for both atoms and

molecules

• Wavelengths are a characteristic

property of a particular substance.

• Spectra are often used to identify

substances, in areas from forensics to
astrophysics.
How Are Atoms “Put Together”?

• Want a model for the atom, based on and consistent with experiments.
• Assume we know atoms contain protons, neutrons, electrons.
• What kind of data can we use?
• Spectra – but these get very complicated
• Ionization  take the atom apart to see how it is put together
• Use the photoelectric effect but instead of using a metal surface use
atoms as targets.
• Shoot high energy photons (UV or X-rays) at atoms, looks for ejected
electrons, and measure kinetic energy of the electrons. This technique
is called Photoelectron Spectroscopy.
Photoelectron Spectroscopy Experiment

Gas
Source

Light
Source
PE Spectrum of H-atoms

UV photons with a wavelength of 10.06 nm are used to eject electrons

from hydrogen atoms. Kinetic energy of the ejected electrons is
10.6 MJ/mol. Find binding energy of the electrons in a H atom.
Solution
Find energy of one mole of photons
hc
E = h =

(6.626 x 10-34 J s)(3 x 108 m / s)
=
10.06 x 10-9 m
= 1.98 x 10-17 J
= 1.19 x 107 J/mol
= 11.9 MJ/mol

Find electron binding energy

KE = 10.6 MJ/mol
Ep = 11.9 MJ/mol
BE = Ep - KE
= (11.9 - 10.6) MJ/mol
BE = 1.3 MJ/mol
PE Spectrum – Helium (2 electrons)

Peak at
# of e–’s detected

2.37 MJ/mol

6 5 4 3 2 1 0
e– Binding Energy (MJ/mol)
PE Spectrum – Neon (10 electrons)

# of e–’s detected

84.5 82.5 6 5 4 3 2 1

e– Binding Energy (MJ/mol)

PE Spectrum - Element?
# of e–’s detected

127 125 10 9 8 7 6 5 4 2 0

e– Binding Energy (MJ/mol)

He, Ne, Ar Energy Levels

–1.52 
–2.37  –2.08 
–2.83 
–4.68 
–24.1 
–31.5 
–84.0 

–309 

He Ne Ar
(Energy in MJ/mol, E’s not drawn to scale!)
Clicker Question
This is the photoelectron
spectrum for which
element? Atomic
numbers are in
parenthesis

A. Na (11)
B. Cl (17) # of e–’s
detected
C. S (16)
D. K (19)
E. Ar (18)
Electron Binding Energy (MJ/mol)
 Shell Model for
Atom
Photoelectron spectra suggest:

• Electrons in atoms go into “shells”

• Low energy shells fill up first, then higher E
• The easiest electron to remove comes from the highest populated shell
• Energy of a shell varies across periodic table.

• A new physics called “Quantum Mechanics” was developed to

provide an understanding of atomic structure.
8-5 Two Ideas Leading to a New Quantum Mechanics

Wave-Particle Duality
•Einstein suggested particle-like
properties of light could explain the
photoelectric effect.
•Diffraction patterns suggest photons
are wave-like.
deBroglie, 1924
Small particles of matter may at times
display wavelike properties.

Louis de Broglie
Nobel Prize 1918
Uncertainty Principle
Curious result of wave interpretation
“Impossible to know both the position and energy (or momentum) of the
electron precisely”
Mathematically:
(x)(p) > h/4
This is a statement of the Heisenberg Uncertainty Principal.
Quantum Mechanics predicts that:
•electrons in atoms can only have certain quantized energies.
•If we measure electron energy precisely, the position CAN’T be
specified
•Electrons show properties of waves AND particles.
•Electrons in atoms are best described as “delocalized waves”
•Information about the energy and position of an electron in an atom is
contained in the “wavefunction”, , of the electron.
Electrons in an atom
• Due to uncertainty principle, the position of electron in an
atom cannot be absolutely determined.

• The probability of finding an electron in a given region of

space around the nucleus can be calculated using the
wavefunction of the electron.

The figure shows an area of

space that an electron may be
found in. This area is called an
“orbital”. As you will find out, there are
several other orbital shapes.
Quantum numbers

• The energy and most probable location of an electron within an atom

is determined by three quantum numbers, n, l, and ml.

• Each electron in an atom is assigned a set of these three quantum

numbers.

• A set of three numbers defines an “orbital”, the wave representation of

the electron, which defines the region of space in which the electron is
most likely to be found. No more than two electrons can occupy each
orbital.
Quantum Numbers
1. n - principal quantum number
influences energy and size of the orbital
n = 1, 2, 3, ...

2. l - azimuthal quantum number

shape of orbital (mainly)
l = 0, 1, 2, ..., (n -1)

3. ml - magnetic quantum number

orientation of orbital (mainly)
ml = -l, ..., 0, ... +l

Combining these rules lets us

find the allowed orbitals
Problem
Orbital designations
Letters are assigned for l values:

l= 0 1 2 3 4 5…
s p d f g h
•So, an orbital with n = 3 and l = 2, would be designated as a 3d orbital.
•Since l = 2, ml = +2, +1, 0, -1, -2 or five values. So there are five
3d orbitals.
Allowed combinations
n l ml # of type of
orbitals orbitals
1 0 0 1 1s
2 0 0 1 2s
1 -1,0,+1 3 2p
3 0 0 1 3s
1 -1,0,+1 3 3p
2 -2,-1, 0,+1,+2 5 3d
Principal Shells and Subshells

FIGURE 8-23
Shells and subshells of a hydrogen atom
Orbital Shapes

These pictures represent the region of space where it is 95% likely that
the electron will be found

s orbitals

FIGURE 8-24
Three representations of the electron probability density for the 1s orbital
 FIGURE 8-28
The three 2p orbitals
 FIGURE 8-30
Representations of the five d orbitals
Clicker Question

Which of the following sets of quantum

numbers is not matched with the orbital
designation.

A. n=1, l = 0: a 1s orbital
B. n=2, l = 0: a 2p orbital
C. n=3, l = 0: a 3s orbital
D. n=3, l = 1: a 3p orbital
E. n=3, l = 2: a 3d orbital
Orbital energy diagram

FIGURE 8-36
Orbital energy-level diagram for the first three electronic shells
Order of filling subshells

The order of filling of electronic subshells

8-9 Electron Spin: A Fourth Quantum
Number

FIGURE 8-32
Electron spin visualized
8-11 Electron Configurations
Aufbau process
Electrons occupy orbitals in a way that
minimizes the energy of the atom.
Pauli exclusion principle
No two electrons can have all four quantum
numbers alike.
Hund’s rule
When orbitals of identical energy (degenerate
orbitals) are available, electrons initially occupy
these orbitals singly.
Representing Electron
Configurations

spdf notation (condensed) 1s2 2s2 2p2

spdf notation (expanded) 1s2 2s2 2px1 2py1

spdf notation

Noble gas core notation [He]2s2 2p2

The Aufbau process
8 - 53
Clicker Question
Which of the following orbital diagrams fails to satisfy the
Pauli Exclusion Principle ?

A.

1s 2s 2p 3s 3p

B.

1s 2s 2p 3s 3p

C.

1s 2s 2p 3s 3p
The Aufbau Process – Sc through Zn
8-12 Electron Configurations and the
Periodic Table

FIGURE 8-38
Clicker Question
Which of the following is the noble gas core notation electron
configuration for chlorine?

A. [Ne]3p7
B. [Ne]3s23p5
C. [Ne]3s23p6
D. [Ne]3s23d5
E. [Ne]3s23p33d2
9-6 Magnetic Properties

 Diamagnetic atoms or ions:

All e- are paired.
Weakly repelled by a magnetic field

 Paramagnetic atoms or ions:

Unpaired e-.
Attracted to an external magnetic field.
Paramagneti
sm

Notice for transition metal ions, first the 4s electrons come off and
then the 3d
Problem
Identify the following atoms/ions as either
paramagnetic or diamagnetic.

a) N
b) Ti2+
c) P
d) Br
Valence
Electrons
–
Those e ’s with highest n value, plus any in partially
filled d or f shells are the valence electrons.
Farthest from the nucleus, highest energies
Most “accessible”
• Determine the chemical properties of an atom
• Elements in a given group of the periodic table
have the same number of valence electrons

How many valence electrons for: N, S, F, and O?

How many valence electrons for: N, S, F, and O?