Chapter 7

Atomic Structure

1
 Light
● Made up of electromagnetic radiation
● Waves of electric and magnetic fields
at right angles to each other.

2
 Parts of a wave
Wavelength Cres
λ t

Amplitud
e
Frequency = number of cycles in one second
Measured in hertz 1 hertz = 1 cycle/second
3
 Frequency = ν

4
 Kinds of EM waves
● There are many
● different λ and ν
● Radio waves, microwaves, x rays
and gamma rays are all examples
● Light is only the part our eyes can
detect
Gamma Radio
Rays waves

5
 The speed of light
● in a vacuum is 2.998 x 108 m/s
●=c
● c = λν
● What is the wavelength of light with a
frequency 5.89 x 105 Hz?
● What is the frequency of blue light
with a wavelength of 484 nm?

6
 In 1900
● Matter and energy were seen as
different from each other in
fundamental ways
● Matter was particles
● Energy could come in waves, with
any frequency.
● Max Planck found that the cooling of
hot objects couldn’t be explained by
viewing energy as a wave.
7
 Energy is Quantized
● Planck found E came in chunks with
size hν
● E = hν
● h is Planck’s constant
● h = 6.626 x 10-34 J s
● these packets of hν are called
quantum

8
 Einstein is next
● Said electromagnetic radiation is
quantized in particles called photons
● Each photon has a quantum of
energy E = hν = hc/λ
● Combine this with E = mc2
● you get the apparent mass of a
photon
● m = h / (λc) - we won’t be solving

9
 Which is it?
● Is energy a wave like light, or a
particle?
● Yes
● Concept is called the Wave-Particle
duality.
● What about the other way, is matter a
wave?
● Yes

10
 How do they know?
● When light passes through, or
reflects off, a series of thinly spaced
lines, it creates a rainbow effect
● because the waves interfere with
each other.

11
 What will an electron do?
● It has mass, so it is matter.
● A particle can only go through one
hole
● A wave goes through both holes
● Light shows interference patterns

● http://youtu.be/DfPeprQ7oGc

12
 What will an electron do?
● An electron does go though both,
and makes an interference pattern.
● It behaves like a wave.
● Led to Schrödingers equation
– We’ll come back to this

● Other matter has wavelengths too

short to notice.

13
 Spectrum
● The range of frequencies present in
light.
● White light has a continuous
spectrum.
● All the colors are possible.
● A rainbow.

14
 Hydrogen spectrum
● Emission spectrum because these are the
colors it gives off or emits
● Called an atomic emission spectrum or
line spectrum.
● There are just a few discrete lines showing

434 656
nm nm

410 486 •Spectrum

15
nm nm
 What this means
● Only certain energies are allowed for
the hydrogen atom.
● Can only give off certain energies.
● Use ΔE = hν = hc / λ
● Energy in the atom is quantized

16
 Niels Bohr
● Developed the quantum model of the
hydrogen atom.
● He said the atom was like a solar
system

17
 The Bohr Ring Atom
● He didn’t know why but only certain
energies (orbits) 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
18
 The Bohr Ring Atom
n=
4n =
3n =
2n =
1

19 • ΔE = -2.178 x 10-18J · Z2 (1/ nf2 - 1/ ni2)

 The Bohr Model
● Doesn’t work
● only works for hydrogen atoms
● electrons don’t move in circles
● the quantization of energy is right,
but not because they are circling like
planets.

20
 The Quantum Mechanical Model
● A totally new approach
● De Broglie said matter could be like a
wave.
● De Broglie said they were like
standing waves.
● The vibrations of a stringed
instrument

21
22
 What’s possible?
● You can only have a standing wave if
you have complete waves.
● There are only certain allowed waves.
● In the atom there are certain allowed
waves called electrons.
● 1925 Erwin Schroedinger described the
wave function of the electron
● A LOT of math, but what is important
are the solutions
23
 Schrödinger’s Equation

● Ψ is the wave function

● Solutions to the equation are called
orbitals.
● These are not Bohr orbits.
● Each solution is tied to a certain
energy
● These are the energy levels
•Animation
24
 There is a limit to what we can
know
● We can’t know how the electron is
moving or how it gets from one
energy level to another.
● The Heisenberg Uncertainty Principle
● There is a limit to how well we can
know both the position and the
momentum of an object.

25
 What does the wave Function
mean?
● nothing.
● it is not possible to visually map it.
● The square of the function is the
probability of finding an electron near a
particular spot.
Ψ2 is the probability distribution
● best way to visualize it is by mapping the
places where the electron is likely to be
found.
26
 Probabilit
y

Distance from
27
nucleus
 28
Sum of all
Probabilities

nucleus
Distance from
 Defining the size
● The nodal surface.
● The size that encloses 90% to the
total electron probability.
● NOT at a certain distance, but a most
likely distance.
● For the first solution it is a a sphere.

29
 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) size
and energy of an orbital
● Has integer values >0

30
 Quantum numbers
● Angular momentum quantum number l
● shape of the orbital
● integer values from 0 to n-1
● l = 0 is called s
● l = 1 is called p
● l =2 is called d
● l =3 is called f
● l =4 is called g
31
 S orbitals

32
 P orbitals

33
 P Orbitals

34
 D orbitals

35
 F orbitals

36
 F orbitals

37
 Quantum numbers
● Magnetic quantum number (m )
l
– integer values between - l and + l
– tells direction in each shape

● Electron spin quantum number (m )

s
– Can have 2 values
– either +1/2 or -1/2

38
 Pauli Exclusion Principle
● In a given atom, no two electrons are
identical (i.e. no two e- can have the
same set of 4 quantum numbers.
● Since only two values of ms are allowed
(-1/2 and +1/2) an orbital can hold only two
electrons and they must have opposite
spins.

39
 The Periodic Table
● Developed independently by German
Julius Lothar Meyer and Russian
Dmitri Mendeleev (1870’s)
● Didn’t know much about atom.
● Put in columns by similar properties.
● Predicted properties of missing
elements.

40
 Aufbau Principle
● Aufbau is German for building up
● As the protons are added one by
one, the electrons fill up hydrogen-
like orbitals.
● Fill up in order of energy

41
 7s 7p
6s 6p 6d 6f
5s 5p 5d 5f
Increasing energy

4s 4p 4d 4f

3s 3p 3d

2s 2p Orbitals available
to a Hydrogen
1s atom
42
 7p 6d
7s 6p 5f
5d
6s 5p 4f
4d
5s
4p
Increasing energy

4s 3d
3p
3s
2p With more
2s electrons, repulsion
changes the energy
1s of the orbitals.
43
 7p 6d
7s 6p 5f
5d
6s 5p 4f
4d
5s
4p
Increasing energy

4s 3d
3p
3s
2p He with 2
2s electrons

1s
44
 7p 6d
7s 6p 5f
5d
6s 5p 4f
4d
5s
4p
Increasing energy

4s 3d
3p
3s
2p
2s

1s
45
 Details
● Valence electrons- the electrons in
the outermost energy levels (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.
● C 1s2 2s2 2p2

46
 Fill from the bottom up following
the arrows
7s 7p 7d 7f
6s 6p 6d 6f
5s 5p 5d 5f • 1s2 2s2 2p6 3s2
4s 4p 4d 4f 3p6 4s2 3d10 4p6
3s 3p 3d 5s2 4d10 5p6 6s2
2s 2p
1s • 13425 electrons
8260
47
 Details
● 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 s&p in the highest
energy level.
● Transition metals are filling the d orbitals

48
 The Shorthand
● Write the symbol of the noble gas
before the element
● Then the rest of the electrons.
● Aluminum - full configuration
● 1s22s22p63s23p1
● Ne is 1s22s22p6
● so Al is [Ne] 3s23p1

49
 The Shorthand

Sn - 50 electrons
The noble gas
before it is Kr
Takes care of 36
Next 5s2
Then 4d10
[ Kr ] 5s2 4d10 5p2
Finally 5p2
[ Kr ] 4d10 5s2 5p2
50
 Electron Configs
● There are two correct ways to write
electron configs
● For Ga
● [Ar]4s23d104p1 (order of filling)
– Written how the periodic table is
structured - easy to find element
● [Ar] 3d104s24p1 (grouped by energy
level)
– Grouped by valence e- - easy to see
what e- are lost when forming a + ion.
51
 Exceptions

● Cr = [Ar] 3d5 4s1

● Half filled orbitals

● Scientists aren’t certain why it
happens
● same for Cu [Ar] 3d10 4s1

52
 More exceptions
● Lanthanum La: [Xe] 5d1 6s2
● Cerium Ce: [Xe] 5d1 4f16s2
● Promethium Pr: [Xe] 4f3 6s2
● Gadolinium Gd: [Xe] 4f7 5d1 6s2
● Lutetium Pr: [Xe] 4f14 5d1 6s2

● We’ll just pretend that all except Cu

53 and Cr follow the rules.
 PES
● Photoelectron Spectroscopy
● a technique which looks at the
energy needed to remove an electron
from an atom or an ion – see
supplemental material
● It can be used to study (and verify)
the electron configuration of atoms
● For us, a lot of it is graph
interpretation
54
 PES
● Here is the graph for hydrogen
– x axis is in MJ/mol

55
 PES
● How does lithium compare to hydrogen?

56
 PES
● Practice: Identify each peak.

57
 PES
● Notice anything?

58
 ● Coulomb’s Law

59
 Effective Nuclear Charge

60
 Effective Nuclear Charge
● The nuclear charge (Z) is simply the number of p+
● Doesn’t explain periodicity of properties
● Outer electrons are said to be “shielded” from the
nucleus by inner electrons
● Effective nuclear charge (Zeff) takes this shielding
into account
● Zeff = #p+ - number of inner e-
Or
Zeff = atomic # - atomic number of previous noble gas
Example
● Zeff for Na = 11 - 10 = +1
● All elements in a group have the same Zeff
61
 Periodic Trends

● With all periodic trends, you need to

not only know them, but be able to
explain them, so keep in mind

● Coulomb’s Law

● Effective Nuclear Charge (Zeff)

62
 Periodic Trends
● Ionization energy is the energy
required to remove an electron from a
gaseous atom
● Highest energy electron removed first.

● First ionization energy (I ) is that

1
required to remove the first electron.
● Second ionization energy (I ) - the
2
second electron
63 ● etc. etc.
 Trends in ionization energy
● for Mg
• I1 = 735 kJ/mole
• I2 = 1445 kJ/mole
• I3 = 7730 kJ/mole
● The effective nuclear charge increases
as you remove electrons.
● It takes much more energy to remove a
core electron than a valence electron
because there is less shielding and
smaller distance (Coulomb’s Law)
64
 Explain this trend
● For Al
• I1 = 580 kJ/mole
• I2 = 1815 kJ/mole
• I3 = 2740 kJ/mole
• I4 = 11,600 kJ/mole

65
 Across a Period
● Generally from left to right, I1
increases because
● there is a greater nuclear charge with
the same shielding and (nearly) the
same distance – Coulomb’s Law
● As you go down a group I1
decreases because electrons are
further away and there is more
shielding
66
 It is not that simple
● Zeff changes as you go across a
period, so will I1
● Half-filled and filled orbitals are
harder to remove electrons from
● here’s what it looks like

67
68
First Ionization energy

Atomic number
69
First Ionization energy

Atomic number
70
First Ionization energy

Atomic number
 Atomic Size
● First problem where do you start
measuring
● The electron cloud doesn’t have a
definite edge.
● They get around this by measuring
more than 1 atom at a time

71
 Atomic Size

}
Radius
Atomic Radius = half the distance between
two nuclei of a diatomic molecule
72
 Trends in Atomic Size
● Influenced by two factors
● Shielding
● More shielding is further away
● Charge on nucleus
● More charge pulls electrons in
closer

73
 Group trends
● As we go down a H
group Li
● Each atom has
Na
another energy
level
K
● So the atoms get
bigger
Rb

74
 Periodic Trends
● As you go across a period the radius
gets smaller.
● Same energy level
● More nuclear charge – stronger
Coulombic interaction
● Outermost electrons are closer

75 Na Mg Al Si P S Cl Ar
 Electron Affinity
● The energy change associated with
adding an electron to a gaseous atom
● High electron affinity gives you energy-
● exothermic
● Increase means “more negative”
● Increase (more - ) from left to right
● Decrease as we go down a group

76
 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.

77
 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.

78
 Configuration of Ions
● Ions almost always have noble gas
configurations
● Na is 1s22s22p63s1
● Forms a 1+ ion - 1s22s22p6
● Same configuration as neon
● Metals lose e-, nonmetals gain e-

79
 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.

80
 Group trends
● Adding energy level
● Ions get bigger as Li+1
you go down Na+1
K+1
Rb+1

Cs+1

81
 Periodic Trends
● Across the period effective nuclear charge
increases so they get smaller (same idea
as atoms)
● Energy level changes between anions and
cations

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

Be
+2 C+4
82
 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

83
 Size of Isoelectronic ions
● Positive ions have more protons so
they are smaller

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

Mg+2
84
 Electronegativity

85
 Electronegativity
● The tendency for an atom to attract
electrons to itself when it is
chemically combined with another
element.
● How “greedy”
● Large electronegativity means it
pulls the electron toward itself.
● Atoms with large negative electron
affinity have larger electronegativity.

86
 Group Trend
● The further down a group more
shielding
● Less attracted (Zeff)
● Low electronegativity.

● For the most part, noble gases are

not part of our EN trend

87
 ● 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

● Metallic character
– Decreases left to right across a period
88 – Increases down a group
 Ionization energy, electronegativity
Electron affinity INCREASE

89
 Atomic size increases,

Ionic size increases

90