CHAPTER 8 - Lecture Notes

CHEM101 F15: Chapter 8: Electrons in Atoms
Electromagnetic Radiation
WaveAmplitude
Wavelength
Low
High
1
General Chemistry: Principles and Modern Applications, Petrucci, Harwood, Herring, Madura, 9th edition, 2007, Pearson Prentice Hall, p. 279

2
Chemistry A Molecular Aprroach, Tro, 1st edition, 2008, Pearson Prentice Hall, p.284

Frequency () in HertzHz or s-1.

Wavelength () in metersm.
cm
m
nm
(10-2 m)
(10-6 m) (10-9 m)
pm
(10-10 m) (10-12 m)
Velocity (c) 2.997925 108 m s-1.
c =
= c/
= c/
3

Electromagnetic Radiation Electromagnetic spectrum
4

Practice Example
When lithium atoms are excited in a flame, they produce strong
intensity 670.8 nm light.
What is the frequency of this radiation?
In which part of the electromagnetic spectrum does this radiation

fall?
Is the radiation visible? If so, what color?

Light as a wave
Constructive interference
Destructive interference
6

Light as a Wave - interferometer design
7

Light as a particle - Quantum Theory
Blackbody Radiation:
Max Planck, 1900

Blackbody Radiation light emission by a heated solid
Classical Physics predicted an increase in intensity of
blackbody radiation at lower wavelengths
Experiment showed a peak and fall-off
General Chemistry: Principles and Modern Applications, Petrucci, Harwood, Herring, Madura, 9th edition, 2007, Pearson Prentice Hall, p. 285,6

Quantum Theory
Max Planck proposed:
Energy, like matter, is discontinuous.

Energy is limited to a discrete set of values; the difference
between any two allowed energies is a quantum of energy
Energy is proportional to the frequency of radiation
E = h
h = Plancks constant = 6.62607 x 10-34 J s
9

Practice Example:
What is the energy of one photon of the 670.8 nm light produced
by lithium atoms?
How much energy is produced from photons of the 670.8 nm light

of two moles of lithium atoms (assume one Li atom produces
one photon)?
10
Light as a particle
Photoelectric effect
Heinrich Hertz, 1888

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

#e- I
KEelectron
11
Light as a particle
Einstein, 1905
The light striking the surface has particlelike qualities - photons
Ephoton = h
E=
hc
Threshold frequency condition:

h =
= the binding energy of the electron,
aka work function
Additional energy of photon is transferred
to the electron as kinetic energy:
h = KEelectron +
Albert Einstein 1905
12

Quantum Theory
Photochemical reactions = chemical reactions induced by light
Example:
O2 + h O + O
1 mol of photons are required to dissociate 1 mol O2

molecules into 2 O atoms
1 mol photons = 6.022 x 1023 photons

13
Practice Example:
The binding energy of the electrons of In metal is 397 kJ/mol. Will
indium metal display the photoelectric effect with UV light? With
infrared light?
14

Atomic Spectra
Hydrogen (g)
Helium (g)
Lithium
Sodium
Potassium
15

Atomic Spectra
Helium
Hydrogen
16

The Bohr Atom
Bohrs postulates for the Hydrogen atom (1913):
1.
The electron moves in circular orbits around the nucleus
2.
The electron has a fixed set of allowed orbits (stationary states)
3.
An electron can pass from one allowed orbit to another; energy is absorbed or
emitted
Picture of Bohr model
Energy of electron:
(RH = 2.18 x 10-18 J)
RH
En = 2
n
Chemistry A Molecular Approach, Tro, 1st
edition, 2008, Pearson Prentice Hall, p.293
17

The Bohr Atom - Energies of Bohr atom orbits
Ground state the lowest allowed energy level (n=1)
Excited state -a higher energy level than the ground state (n=2,3,4,)
Energy-level diagram
Balmer Series
Lymon Series
18

The Bohr Atom
Electrons can move from
one energy-level to another:
DEatom = E photon
1
RH RH
1
1
18
DEatom = E f Ei = 2 2 = RH 2 2 = 2.179 10 J 2 2
n n
n n
nf
ni
i
f
f
i
DEatom = h
Note that the sign of DE indicates energy is being emitted or absorbed by the atom
19
Chemistry A Molecular Approach, Tro, 1st


The Bohr Atom - Spectroscopy and the Bohr model
Emission Spectroscopy
Absorption Spectroscopy
20

Example:
Calculate the wavelength of light that is absorbed when a ground state electron in
the hydrogen atom moves to the second excited state (n=3).
Step 1: Calculate the energy associated with the transition of the electron from n=1
to n=3.
1 1
1
1
1 1
DEatom = E f Ei = RH 2 2 = RH 2 2 = RH = RH (0.8889)
n n
1 3
1 9
f
i
= 2.179 10 18 J (0.8889) = 1.937 10 18 J
Step 2: Use the energy calculated in step 1 to find the wavelength of light
absorbed.
DEatom = E photon = h
hc (6.626 1034 Js)(2.9979 108 ms 1 )
7
= =
=
=
1
.
026
10
m
18
DE
1.937 10 J
c
21

Practice Example
Calculate the frequency of the photon absorbed for the n=2 to n=4
transition of Hydrogen.
22

Practice Example
An electron in the n=6 level of the hydrogen atom relaxes to a
lower energy level, emitting light of = 93.8 nm. Find the
principal level to which the electron relaxed.
23

The Bohr Atom
Ionization energy and the Bohr model
To ionize an atom, we remove an electron completely

In terms of the Bohr model for Hydrogen, this means transporting
the electron to the farthest orbit/highest Energy from the nucleus, or
n=
We calculate the ionization energy using the transition from n=1 to
n=
1
1 1
DE = RH 2 2 = RH = RH 1 0 = RH
n n
1
f
i
24

The Bohr Atom
Limitations of the Bohr model
The Bohr model works for any one-electron atom (Hydrogenlike atom)
H
He+
Li2+
Be3+
etc.
Include the nuclear charge (atomic number) in the energy-level

expression to determine which Hydrogen-like species is involved:
Z 2 RH
En =
n2
However, the Bohr model does NOT work for systems that have
more than one electron
25

Example:
The emission spectrum to the right shows all
the lines resulting from transitions to the
ground state from higher energy states for a
one-electron species.
Which transitions on the
corresponding energy diagram
result in lines A and B in the
emission spectrum?
n=
n=6
n=5
n=4
n=3
5 1 4 1
n=3 to n=1
3 1
n=2 to n=1
2 1
DE = E5-E1
DE = E4-E1
DE = E3-E1
Energy
n=2
DE = E2-E1
Smallest energy difference
= longest wavelength
n=1
26

Practice Example:
The emission spectrum to the right shows all
the lines resulting from transitions to the
ground state from higher energy states for a
one-electron species.
If line A has a wavelength of 10.8 nm, what is the identity of the one-electron species?
27

Quantum Mechanics
Two ideas leading to Quantum Mechanics were considered in the 1920s
1. Wave-Particle Duality (de Broglie)
Wave-Particle Duality
Einstein suggested particle-like properties of
light could explain the photoelectric effect.
Diffraction patterns suggest photons
are wave-like.
de Broglie, 1924
Small particles of matter may at times display
wavelike properties.
h
h
p = momentum
= =
p mv
p = mv (mass x velocity)
If mass or velocity are small, the deBroglie
wavelength is larger
Louis de Broglie
Nobel Prize 1918
28
Quantum Mechanics
Two ideas leading to Quantum Mechanics were considered in the
1920s
2. The Heisenberg Uncertainty Principle (Werner Heisenberg)
h
Dx Dp = Dx mDu =
4
Heisenberg and Bohr
29

Practice Example:
Calculate the de Broglie wavelength of a 145-g baseball traveling
at 168 km/h.
What is the uncertainty in the position of this baseball if the

uncertainty in its velocity is 0.01 km/h?
30

Practice Example:
Calculate the de Broglie wavelength of an electron traveling at
2.05 x 106 m/s 3.1 x 104 m/s (masselectron=9.109x10-31kg)
What is the uncertainty in the position of this electron?
31

Quantum Mechanics
Wave functions of the Hydrogen atom
We cannot know both the position and the energy of

an electron simultaneously (Heisenberg Principle)
We choose to solve the problem mathematically such that
we will exactly know the ENERGY of the electron, but
NOT its position
We can only know the region in space where an electron
PROBABLY is; the orbital
32

Wave Mechanics
Standing waves.
Nodes do not undergo displacement.
2L
=
, n = 1, 2, 3
n
33

Wave Mechanics - Wave functions (bound harmonic functions)
, psi, the wave function.

Should correspond to a
standing wave within the
boundary of the system being
described.
Particle in a box.
=
2
n x
sin
L
L
34

Wave Mechanics - Wave functions
, psi, the wave function.

Does not have physical
meaning
2 gives the electron

probability density
the probability of finding an
electron in a particular
location
General Chemistry: Principles and Modern Applications, Petrucci, Harwood,

Herring, Madura, 9th edition, 2007, Pearson Prentice Hall, p. 302
35

Wave Mechanics
Wave functions of the Hydrogen atom (three-dimensionalize the particle
in a box; the particle is an electron; the box is the atom; and more)
Schrdinger, 1927
E = H
H (x,y,z) or H (r,,)
(r,,) = R(r) Y(,)

R(r) is the radial wave function.
Y(,) is the angular wave function.
36
General Chemistry: Principles and Modern Applications, Petrucci, Harwood, Herring, Madura, 9th edition, 2007, Pearson Prentice Hall, p. 303,7

Atomic Orbitals
The wavefunctions of the Hydrogen atom have no physical meaning
The square of the wavefunction, 2, describes the probability density
distribution
We can look at 2 to determine the shape of the region where an
electron will be found, the orbital
Each orbital is assigned a set quantum numbers to describe its:
size
shape
orientation
37

Quantum numbers - Assigning quantum numbers
Principal quantum number, n
n is a positive, nonzero integer; n = 1,2,3,

principal shell
Distance from the nucleus
Orbital angular momentum quantum number,
is zero or a positive integer; n-1

subshell
Shape of the orbital
=0 is
=1 is
=2 is
=3 is
s
p
d
f
Magnetic quantum number, m
m is a negative or positive integer or zero

m ranges from to +
Orientation of orbital in space
38

Quantum numbers
39

Quantum numbers - Energies of hydrogen atom orbitals
1
En = 2.178 10 2 J
n
18
(Same as Bohr formula)

Orbitals with the same n value are degenerate (have the same energy)
40

Practice Example:
What type of orbital is designated by the following quantum
numbers?
n = 5, = 1, m = 0
n = 4, = 2, m = -2
n = 2, = 0, m = 0
41

Atomic Orbitals
s orbitals ( = 0) are spherically shaped
Number of angular nodes = 0 ( a node is a point where the probability

density, wave function and the radial distribution all go through zero)
42

Atomic Orbitals
p orbitals ( = 1) are dumbbell shaped
Number of angular nodes = 1
43

Atomic Orbitals
p orbitals have three orientations in space (ml = -1, 0, +1)
Chemistry A Molecular Aprroach, Tro, 1st

44

Atomic Orbitals
d orbitals (l = 2) are (mostly) cloverleaf shaped
Number of angular nodes = 2
d orbitals have five orientations in space (ml = -2, -1, 0, +1, +2)

45

Atomic Orbitals
f orbitals (l = 3) have 3 angular nodes
f orbitals have seven orientations in space (ml = -3, -2, -1, 0, +1, +2, +3)

46

Atomic Orbitals
Atomic orbitals and the principal
quantum number
As n increases, the probability

density distribution extends
further away from the nucleus
Each time n increases by 1,

another radial node appears
Radial probability distributions

show the probability of finding an
electron in a sphere of radius r:
4r2x R2(r)

47

Practice Examples:
Write an acceptable value for each of the missing quantum

numbers:
n = 3, l = ?, ml = 2
n = ?, l = 2, ml = 1
n = ?, l = 0, ml = ?
How many orbitals have the values n = 4 and l = 3?

How would the 3p orbitals differ from the 2p orbitals?
Which electron, on average, is closer to the nucleus: an
electron in a 3s orbital or an electron in a 4s orbital?
48

Atomic Orbitals - Angular and Radial Nodes of Atomic Orbitals
The nodes of a specific orbital can be related to n
n = number of radial nodes + number of angular nodes + 1
Recall that the number of angular nodes:
0 for an s orbital
1 for a p orbital
2 for a d orbital
Recall that the number of radial nodes increases by 1 as n increases by 1:
Example: how many angular and radial nodes are present in a 4d orbital?
d orbitals contain 2 angular nodes

n = radial nodes + 2 + 1; Since n = 4, there is 1 radial node
49

Practice Example:
Identify the orbital that has:
2 radial nodes and 1 angular node
5 radial nodes and 0 angular nodes
1 radial nodes and 3 angular nodes
Which d orbital would be represented by the following

probability distribution?
50
Electron Spin - The fourth quantum number

George Uhlenbeck and Samuel Goudsmit, 1925, proposed that an
electron acts as if its spins
An electron can spin in two different directions
We give the electron spin the quantum number ms and is either
1
1
ms = or
2
2
A spinning electron
generates a magnetic field
51

Electron Spin
The Stern-Gerlach experiment
52

Electron Spin - The four quantum numbers for the Hydrogen atom
Each orbital contains up to two electrons with opposite spin
Example:
n = 2, = 0, m = 0, ms = +1/2
indicates an electron in a 2s orbital
Because each orbital can hold two electrons:
Shell (n)
1
2
3
4
Subshell(s)
s
s, p
s, p, d
s, p, d, f
Orbitals
Electron capacity
1
2
4 (1s and 3p)
8
9 (1s, 3p, 5d)
18
16 (1s,3p,5d,7f)
32
53

Multielectron Atoms
The Schrodinger equation and solutions for orbital shapes all apply to one-electron
systems
When atoms contain more than one electron, corrections for repulsions between
electrons must be accounted for
Penetration and Shielding
Electrons in orbitals closer to the nucleus shield electrons farther away from feeling
the attraction to the positively charged nucleus of the atom
Chemistry A Molecular Aprroach,

Tro, 1st edition, 2008, Pearson
Prentice Hall, p. 324
54

Multielectron Atoms
Effective Nuclear Charge, Zeff
The nuclear charge that an electron actually experiences

Smaller than the effective nuclear charge if no shielding occurs
Chemistry A Molecular Aprroach,

Tro, 1st edition, 2008, Pearson
Prentice Hall, p. 324
55

Multielectron Atoms
Because of shielding, the energy levels for

the same n of different orbitals are
no longer degenerate
s orbitals have a higher Zeff, are held

more tightly, and have lower
energies than p orbitals
s orbitals have a higher Zeff and have

lower energies than d orbitals
56
Chemistry A Molecular Aprroach, Tro, 1st edition,

2008, Pearson Prentice Hall, p. 5

Multielectron Atoms
Orbital energies of multielectron atoms
57

Electron Configurations
An electron configuration for an atom shows the particular orbitals that
are occupied for the atom
Example, the electron configuration for the hydrogen atom is 1s1:
58
Chemistry A Molecular Aprroach, Tro, 1st edition, 2008, Pearson Prentice Hall, p. 321

Assigning electrons to orbitals
1.
Electrons occupy orbitals in a way that minimizes the energy of the

atom.
The order in which orbitals are filled:
1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s 4f 5d 6p 7s 5f 6d 7p
2.
No two electrons in an atom have the same four quantum number

The Pauli Exclusion Principle
3.
When orbitals of identical energy are available, electrons occupy

these orbitals singly Hunds Rule
59
Assigning electrons to orbitals
1.
Electrons occupy orbitals in a way that minimizes the energy of

the atom.
The order in which orbitals are filled:
1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s 4f 5d 6p 7s 5f 6d 7p
Simple visual device
60

Representing electron configurations: Example - carbon

spdf notation (condensed): 1s22s22p2
spdf notation (expanded): 1s22s22px12py1
orbital diagram:
valence electron method: [He]2s22p2

Also correct to write the valence shell configurations with
the lowest n first
61

The aufbau process assign electron configurations to elements in order
of increasing atomic number
Example: Elements 7-10:
62

Example: Elements 21-30:
63

Electron Configurations and the Periodic Table
The organization of the Periodic Table is based on electron
configurations
Also see Appendix D (Page A-17)

for a listing of all electron
configurations
64

Electron Configurations and the Periodic Table
Recall that elements in the same groups have similar chemical

properties
Elements in the same group have the SAME ELECTRONIC

CONFIGURATIONS in their valence shells
Example Group IIA (2)

Be 1s22s2
Mg 1s22s22p63s2
Ca 1s22s22p63s23p64s2
Sr 1s22s22p63s23p64s23d104p65s2
Ba 1s22s22p63s23p64s23d104p65s24d105p66s2
Ra 1s22s22p63s23p64s23d104p65s24d105p66s24f145d10
6p67s2
All of these elements have two electrons in an s orbital in their valence

65
shells (ns2)

Practice Example:
Write the electron configuration for Sn in:
Condensed spdf form
Orbital diagram form with valence electrons
Condensed spdf form with valence electrons
66

Practice Example:
Which of the following is the correct orbital diagram for the
ground-state electron configuration of phosphorus? What is
wrong with the others?
67

Practice Example:
Which of the following electron configurations corresponds to the
ground state and which to an excited state?
68

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CHEM101 F15: Chapter 8: Electrons in Atoms

CHEM101 F15: Chapter 8: Electrons in Atoms

CHEM101 F15: Chapter 8: Electrons in Atoms

Frequency () in HertzHz or s-1.

Velocity (c) 2.997925 108 m s-1.

CHEM101 F15: Chapter 8: Electrons in Atoms

CHEM101 F15: Chapter 8: Electrons in Atoms

In which part of the electromagnetic spectrum does this radiation

CHEM101 F15: Chapter 8: Electrons in Atoms

CHEM101 F15: Chapter 8: Electrons in Atoms

CHEM101 F15: Chapter 8: Electrons in Atoms

Max Planck, 1900

CHEM101 F15: Chapter 8: Electrons in Atoms

Max Planck proposed:

Energy, like matter, is discontinuous.

CHEM101 F15: Chapter 8: Electrons in Atoms

How much energy is produced from photons of the 670.8 nm light

CHEM101 F15: Chapter 8: Electrons in Atoms

Heinrich Hertz, 1888

> o threshold frequency

CHEM101 F15: Chapter 8: Electrons in Atoms

Threshold frequency condition:

Albert Einstein 1905

CHEM101 F15: Chapter 8: Electrons in Atoms

1 mol of photons are required to dissociate 1 mol O2

1 mol photons = 6.022 x 1023 photons

CHEM101 F15: Chapter 8: Electrons in Atoms

CHEM101 F15: Chapter 8: Electrons in Atoms

CHEM101 F15: Chapter 8: Electrons in Atoms

CHEM101 F15: Chapter 8: Electrons in Atoms

CHEM101 F15: Chapter 8: Electrons in Atoms

CHEM101 F15: Chapter 8: Electrons in Atoms

Chemistry A Molecular Approach, Tro, 1st

CHEM101 F15: Chapter 8: Electrons in Atoms

CHEM101 F15: Chapter 8: Electrons in Atoms

= 2.179 10 18 J (0.8889) = 1.937 10 18 J

CHEM101 F15: Chapter 8: Electrons in Atoms

CHEM101 F15: Chapter 8: Electrons in Atoms

CHEM101 F15: Chapter 8: Electrons in Atoms

To ionize an atom, we remove an electron completely

CHEM101 F15: Chapter 8: Electrons in Atoms

Include the nuclear charge (atomic number) in the energy-level

CHEM101 F15: Chapter 8: Electrons in Atoms

CHEM101 F15: Chapter 8: Electrons in Atoms

CHEM101 F15: Chapter 8: Electrons in Atoms

CHEM101 F15: Chapter 8: Electrons in Atoms

Heisenberg and Bohr

CHEM101 F15: Chapter 8: Electrons in Atoms

What is the uncertainty in the position of this baseball if the

CHEM101 F15: Chapter 8: Electrons in Atoms

What is the uncertainty in the position of this electron?

CHEM101 F15: Chapter 8: Electrons in Atoms

We cannot know both the position and the energy of

CHEM101 F15: Chapter 8: Electrons in Atoms

CHEM101 F15: Chapter 8: Electrons in Atoms

, psi, the wave function.

CHEM101 F15: Chapter 8: Electrons in Atoms

, psi, the wave function.

2 gives the electron

General Chemistry: Principles and Modern Applications, Petrucci, Harwood,

CHEM101 F15: Chapter 8: Electrons in Atoms

(r,,) = R(r) Y(,)

CHEM101 F15: Chapter 8: Electrons in Atoms