Larry Brown

Tom Holme

www.cengage.com/chemistry/brown

Chapter 6
The Periodic Table
and Atomic Structure

Jacqueline Bennett • SUNY Oneonta

Chapter Objectives
• Describe similarities and differences between various light
sources.

• Describe waves in terms of frequency, wavelength, and

amplitude.

• Interconvert between the frequency, wavelength, and

amplitude of light and relate those those quantities to
characteristics such as color and brightness.

• Describe the photoelectric effect by stating what sort of

experiment is involved and what results are seen.

2
Chapter Objectives
• Explain how the results of the photoelectric effect experiment
are consistent with a photon model of light.

• Use Planck’s equation to calculate the energy of a photon

from its wavelength or frequency.

• Use ideas about conservation of energy to explain how the

observation of atomic spectra implies that atoms have
quantized energies.

3
Chapter Objectives
• Use an energy-level diagram to predict the wavelengths or
frequencies of light that an atom will absorb or emit, or use
the observed wavelengths or frequencies to determine the
allowed energy levels.

• Describe similarities and differences between the Bohr model

and the quantum mechanical model of atomic structure.

• Recognize how quantum numbers arise as a consequence of

the wave model.

• Define the term orbital.

4
Chapter Objectives
• Identify an orbital (as 1s, 3p, etc.) from its quantum numbers
or vice versa.

• List the number of orbitals of each type (1s, 3p, etc.) in an

atom.

• Sketch the shapes of s and p orbitals and recognize orbitals

by their shapes.

• Rank various orbitals in terms of size and energy.

5
Chapter Objectives
• Use the Pauli exclusion principle and Hund’s rule to write
electron configurations for atoms and ions of main group
elements.

• Explain the connection between valence electron

configurations and the periodic table.

• Define the following properties of atoms: atomic radius,

ionization energy, and electron affinity.

• State how the above properties vary with position in the

periodic table.

6
Incandescent and Fluorescent Lights

• When metals are heated, they glow (incandescence)

• The specific color of light emitted depends on the

temperature of the metal.

• Low temperature emission is red, higher temperature

emission is orange, and eventually the emission becomes
white.

• Light bulbs produce light by heating a metal filament with

electricity.

7
Incandescent and Fluorescent Lights

• Tungsten metal glows white

when electrical current
passes through the filament.

• Filament temperature is
about 4000oF.

8
Incandescent and Fluorescent Lights

• Gases can be made to emit light when an arc of electricity

passes through a poorly conducting gas.
• The electrical arc excites gas molecules, which emit light
that then interacts with the phosphor to reemit light of
many different possible colors. (fluorescence)

9
The Electromagnetic Spectrum
• Visible light is a small portion of
the electromagnetic radiation
spectrum detected by our eyes.
• Electromagnetic radiation includes
radio waves, microwaves and X-
rays.
• Described as a wave traveling
through space.
• There are two components to
electromagnetic radiation, an
electric field and magnetic field.

10
The Wave Nature of Light
• Wavelength, , is the distance
between two corresponding
points on a wave.
• Amplitude is the size or
“height” of a wave.
• Frequency, , is the number of
cycles of the wave passing a
given point per second, usually
expressed in Hz.

11
The Wave Nature of Light
• The fourth variable of light is velocity.

• All light has the same speed in a vacuum.

• c = 2.99792458 x 108 m/s

• The product of the frequency and wavelength is the speed

of light.

c  
• Frequency is inversely proportional to wavelength.

12
The Wave Nature of Light
• Refraction is the bending of light when it passes from one
medium to another of different density.
• Speed of light changes.
• Light bends at an angle depending on its wavelength.
• Light separates into its component colors.

13
The Wave Nature of Light
• Electromagnetic radiation can be categorized in terms of
wavelength or frequency.

• Visible light is a small portion of the entire electromagnetic

spectrum.

14
Example Problem 6.1
• Neon lights emit an orange-red colored glow. This light has a
wavelength of 670 nm. What is the frequency of this light?

15
The Particulate Nature of Light
• Photoelectric effect: light striking a metal surface generates
photoelectrons.

• The light’s energy is transferred to electrons in metal.

• With sufficient energy, electrons “break free” of the metal.

• Electrons given more energy move faster (have higher

kinetic energy) when they leave the metal.

16
The Particulate Nature of Light
• Photoelectric effect is used
in photocathodes.

• Light strikes the cathode

at frequency . Electrons
are ejected if  exceeds
the threshold value 0.

• Electrons are collected

at the anode.

• Current flow is used to

monitor light intensity.

17
Photoelectric Experiments

a) For  > 0, the number of electrons

emitted is independent of frequency.
Value of 0 depends on metal used.

b) As light intensity increases, the

number of photoelectrons increases.

c) As frequency increases, kinetic

energy of emitted electrons increases
linearly.

d) The kinetic energy of emitted

electrons is independent of light
intensity.

18
The Particulate Nature of Light
• The photoelectric effect is not explained using a wave description
but is explained by modeling light as a particle.

• Wave-particle duality - depending on the situation, light is best

described as a wave or a particle.

• Light is best described as a particle when light is imparting

energy to another object.

• Particles of light are called photons.

• Neither waves nor particles provide an accurate description of

all the properties of light. Use the model that best describes the
properties being examined.

19
The Particulate Nature of Light
• The energy of a photon (E) is proportional to the frequency
().

• and is inversely proportional to the wavelength ().

• h = Planck’s constant = 6.626 x 10-34 J s

hc
E  h 


20
Example Problem 6.2
• The laser in a standard laser printer emits light with a
wavelength of 780.0 nm. What is the energy of a photon of
this light?

21
The Particulate Nature of Light
• Binding Energy - energy holding an electron to a metal.

• Threshold frequency, o - minimum frequency of light

needed to emit an electron.

• For frequencies below the threshold frequency, no electrons

are emitted.

• For frequencies above the threshold frequency, extra

energy is imparted to the electrons as kinetic energy.
• Ephoton = Binding E + Kinetic E

• This explains the photoelectric effect.

22
Example Problem 6.3
• In a photoelectric experiment, ultraviolet light with a
wavelength of 337 nm was directed at the surface of a piece
of potassium metal. The kinetic energy of the ejected
electrons was measured as 2.30 x 10-19 J. What is the
electron binding energy for potassium?

23
Atomic Spectra
• Atomic Spectra: the particular pattern of wavelengths
absorbed and emitted by an element.

• Wavelengths are well separated or discrete.

• Wavelengths vary from one element to the next.

• Atoms can only exist in a few states with very specific

energies.

• When light is emitted, the atom goes from a higher energy

state to a lower energy state.

24
Atomic Spectra

• Electrical current dissociates molecular H2 into

excited atoms which emit light with 4 wavelengths.
25
Example Problem 6.4
• When a hydrogen atom undergoes a transition from E3 to E1,
it emits a photon with  = 102.6 nm. Similarly, if the atom
undergoes a transition from E3 to E2, it emits a photon with  =
656.3 nm. Find the wavelength of light emitted by an atom
making a transition from E2 to E1.

26
The Bohr Atom
• Bohr model - electrons orbit the
nucleus in stable orbits.
Although not a completely
accurate model, it can be used
to explain absorption and
emission.
• Electrons move from low
energy to higher energy
orbits by absorbing energy.
• Electrons move from high
energy to lower energy
orbits by emitting energy.
• Lower energy orbits are
closer to the nucleus due to
electrostatics.

27
The Bohr Atom
• Excited state: grouping of electrons that is not at the lowest
possible energy state.

• Ground state: grouping of electrons that is at the lowest

possible energy state.

• Atoms return to the ground state by emitting energy as

light.

28
The Quantum Mechanical Model of the Atom

• Quantum mechanical model replaced the Bohr model of the

atom.

• Bohr model depicted electrons as particles in circular

orbits of fixed radius.

• Quantum mechanical model depicts electrons as waves

spread through a region of space (delocalized) called an
orbital.

• The energy of the orbitals is quantized like the Bohr

model.
29
The Quantum Mechanical Model of the Atom

• Diffraction of electrons shown in 1927.

• Electrons exhibit wave-like behavior.

• Wave behavior described using a wave function, the

Schrödinger equation.

• H is an operator, E is energy and  is the wave function.

H  E

30
Potential Energy and Orbitals
• Total energy for electrons includes potential and kinetic
energies.
• Potential energy more important in describing atomic
structure; associated with coulombic attraction between
positive nucleus and negative electrons.

• Multiple solutions exist for the wave function for any given
potential interaction.
• n is the index that labels the different solutions.

H n  E n
31
Potential Energy and Orbitals
• n can be written in terms of two components.

• Radial component, depends on the distance from the

nucleus.

• Angular component, depends on the direction or

orientation of electron with respect to the nucleus.

32
Potential Energy and Orbitals
• The wave function may have positive and negative signs in
different regions.
• Square of the wave function, 2, is always positive and
gives probability of finding an electron at any particular
point.

• Each solution of the wave function defines an orbital.

• Each solution labeled by a letter and number combination:
1s, 2s, 2p, 3s, 3p, 3d, etc.
• An orbital in quantum mechanical terms is actually a
region of space rather than a particular point.

33
Quantum Numbers
• Quantum numbers - solutions to the functions used to solve
the wave equation.

• Quantum numbers used to name atomic orbitals.

• Vibrating string fixed at both ends can be used to illustrate

a function of the wave equation.

34
Quantum Numbers
• A vibrating string can be
written in terms of amplitude
A, distance along the string
x, and length of the string L.

• A string fixed at both ends is

an example of how multiple
waves can satisfy a
particular set of conditions.
n x
 n (x)=Asin
L

35
Quantum Numbers
• When solving the Schrödinger equation, three quantum
numbers are used.

• Principal quantum number, n (n = 1, 2, 3, 4, 5, …)

• Secondary quantum number, l

• Magnetic quantum number, ml

36
Quantum Numbers
• The principal quantum number, n, defines the shell in which a
particular orbital is found.

• n must be a positive integer

• n = 1 is the first shell, n = 2 is the second shell, etc.

• Each shell has different energies.

37
Quantum Numbers
• The secondary quantum number, l, indexes energy
differences between orbitals in the same shell in an atom.
• l has integral values from 0 to n-1.
• l specifies subshell
• Each shell contains as many l values as its value of n.

38
Quantum Numbers
• The energies of orbitals are specified completely using only
the n and l quantum numbers.

• In magnetic fields, some emission lines split into three,

five, or seven components.

• A third quantum number describes splitting.

39
Quantum Numbers
• The third quantum number is the magnetic quantum number,
ml.

• ml has integer values.

• ml may be either positive or negative.

• ml’s absolute value must be less than or equal to l.

• For l = 1, ml = -1, 0, +1

40
Quantum Numbers

• Note the relationship between number of orbitals

within s, p, d, and f and ml. 41
Example Problem 6.5
• Write all of the allowed sets of quantum numbers (n, l, and ml)
for a 3p orbital.

42
Visualizing Orbitals
• Wave functions for the first five
orbitals of hydrogen.

• The wave function is written in

spherical polar coordinates with
the nucleus at the origin.

• Point in space defined by

radius r, and angles  and .
• r determines the orbital size.
•  and  determine the orbital
shape.

43
Visualizing Orbitals
• A point in space defined by
radius r, and angles  and .

• Chemists usually think of

orbitals in terms of pictures.

• The space occupied by an

orbital is a 90% probability
of finding an electron.

• A plot of the angular part of

the wave function gives the
shape of the corresponding
orbital.

44
Visualizing Orbitals

• s orbitals are spherical

• p orbitals have two lobes separated by a nodal plane.
• A nodal plane is a plane where the probability of finding an
   electron is zero (here the yz plane).
• d orbitals have more complicated shapes due to the presence
of two nodal planes.
45
Visualizing Orbitals
• Nodes are explained using the Uncertainty Principle.

• It is impossible to determine both the position and

momentum of an electron simultaneously and with
complete accuracy.

• An orbital depicts the probability of finding an electron.

• The radial part of the wave function describes how the

probability of finding an electron varies with distance from the
nucleus.
• Spherical nodes are generated by the radial portion of the
wave function.
46
Visualizing Orbitals

• Cross sectional views of the 1s, 2s, and 3s orbitals.

47
Visualizing Orbitals
• Electron density plots for 3s,
3p, and 3d orbitals showing
the nodes for each orbital.

48
Visualizing Orbitals

• Chemistry of halogen lights

is explained by a quantum
mechanical model of the
halogens.

• Tungsten is deposited
on the filament following
reaction with a halogen.

49
The Pauli Exclusion Principle and
Electron Configurations

• The spin quantum number, ms, determines the number of

electrons that can occupy an orbital.

• ms = ±1/2

• Electrons described as “spin up” or “spin down”.

• An electron is specified by a set of four quantum numbers.

50
The Pauli Exclusion Principle and
Electron Configurations

• Pauli Exclusion Principle - no two electrons in an atom may

have the same set of four quantum numbers.

• Two electrons can have the same values of n, l, and ml,

but different values of ms.

• Two electrons maximum per orbital.

• Two electrons occupying the same orbital are spin paired.

51
Orbital Energies and Electron Configurations

• Electrons in smaller orbitals are held more tightly and have

lower energies.

• Orbital size increases as the value of n increases.

• True for hydrogen atoms, but not entirely true for

multielectron atoms.

• As nuclear charge increases, orbital size decreases.

• Electrons interact with other electrons as well as the

positively charged nucleus.

52
Orbital Energies and Electron Configurations

• For electrons in larger orbitals, the charge “felt” is a

combination of the actual nuclear charge and the offsetting
charge of electrons in lower orbitals.

• The masking of the nuclear charge is called shielding.

• Shielding results in a reduced, effective nuclear charge.

53
Orbital Energies and Electron Configurations

• Effective nuclear charge

allows for understanding of the
energy differences between
orbitals.

• 2s orbital: the small local

maximum close to the
nucleus results in an
electron with a higher
effective nuclear charge.

• 2p orbital: lacks the local

minimum close to the
nucleus of the 2s orbital.
• Lower effective nuclear
charge for 2p electrons.
54
Orbital Energies and Electron Configurations

• The energy ordering for atomic orbitals is 1s, 2s, 2p, 3s, 3p,
4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, and 7p.

• An orbital’s size and penetration when treated

quantitatively produces the order of filling represented.

• Electronic configurations are written in order of energy for

atomic orbitals.

55
Hund’s Rule and the Aufbau Principle

• Aufbau principle - when filling orbitals, start with the lowest

energy and proceed to the next highest energy level.

• Hund’s rule - within a subshell, electrons occupy the

maximum number of orbitals possible.

• Electron configurations are sometimes depicted using boxes

to represent orbitals. This depiction shows paired and
unpaired electrons explicitly.

56
Example Problem 6.6
• What is the electron configuration for the sulfur atom?

57
Hund’s Rule and the Aufbau Principle

• A simplified depiction uses superscripts to indicate the

number of electrons in an orbital set.

• 1s2 2s2 2p2 is the electronic configuration for carbon.

• Noble gas electronic configurations are used as a shorthand

for writing electronic configurations.

• Relates electronic structure to chemical bonding.

• Electrons in outermost occupied orbitals give rise to
chemical reactivity of an element.
• [He] 2s2 2p2 is the shorthand for carbon

58
Hund’s Rule and the Aufbau Principle

• The inner electrons, which lie closer to the nucleus, are referred
to as core electrons.

• Core electrons can be represented by the noble gas with the

same electronic configuration.

• The outer electrons are usually referred to as valence electrons.

• Valence electrons are shown explicitly when a noble gas

shorthand is used to write electronic configurations.

• Valence electrons determine reactivity.

59
Example Problem 6.7
• Rewrite the electron configuration for sulfur using the
shorthand notation.

60
The Periodic Table and Electron Configurations

• The periodic table and the electronic configurations

predicted by quantum mechanics are related.

• The periodic table is broken into s, p, d, and f blocks.

• Elements in each block have the same subshell for the

highest electron.

• Structure of periodic table can be used to predict

electronic configurations.

61
The Periodic Table and Electron Configurations

• The shape of the periodic table can be broken down into blocks
according to the type of orbital occupied by the highest energy
electron in the ground state.
• We find the element of interest in the periodic table and write its
core electrons using the shorthand notation with the previous
rare gas element. Then we determine the valence electrons by
noting where the element sits within its own period in the table.
62
Example Problem 6.8
• Use the periodic table to determine the electron configuration
of tungsten (W), which is used in the filaments of most
incandescent lights.

63
Periodic Trends in Atomic Properties

• Using the understanding of orbitals and atomic structure, it is

possible to explain some periodic properties.

• Atomic size

• Ionization energy

• Electron affinity

64
Atomic Size
• The shell in which the valence electrons are found affects
atomic size.
• The size of the valence orbitals increases with n, so size
must increase from top to bottom for a group.

• The strength of the interaction between the nucleus and the

valence electrons affects atomic size.
• The effective nuclear charge increases from left to right
across a period, so the interaction between the
electrons and the nucleus increases in strength.
• As interaction strength increases, valence electrons
are drawn closer to the nucleus, decreasing atomic
size.
65
Atomic Size
• Graph showing atomic
radius as function of atomic
number.

66
Example Problem 6.9
• Using only the periodic table, rank the following elements in
order of increasing size: Fe, K, Rb, S, and Se.

67
Ionization Energy
• Ionization energy - the energy required to remove an electron
from a gaseous atom, forming a cation.
• Formation of X+ is the first ionization energy, X 2+ would be the
second ionization energy, etc.


X(g) 
 X (g) + e +

• Effective nuclear charge increases left to right across a

period.
• The more strongly held an electron is, the higher the
ionization energy must be.
• As valence electrons move further from the nucleus, they
become easier to remove and the first ionization energy
becomes smaller.
68
Ionization Energy

• Graph of the first ionization energy (in kJ/mol) vs.

atomic number for the first 38 elements.
69
Ionization Energy
• From nitrogen to oxygen, there is a slight decrease in
ionization energy.
• Nitrogen has a half-filled p subshell.
• Oxygen has a pair of p electrons in one 2p orbital.
• Ionization of oxygen relieves electron-electron repulsion,
lowering its ionization energy.

• Ionization energies increase with successive ionizations for a

given element.
• Effective nuclear charge for valence electrons is larger for
the ion than the neutral atom.

• Filled subshells of electrons are difficult to break up, which is

why it is difficult to remove electrons from noble gases.
70
Ionization Energy

• The first four ionization energies in kJ/mol for

elements Z = 1 to 9.
71
Ionization Energy

• The first four ionization energies in kJ/mol for elements Z = 10

to 18.
72
Example Problem 6.10
• Using only the periodic table, rank the following elements in
order of increasing ionization energy: Br, F, Ga, K, and Se.

73
Electron Affinity
• Electron affinity - energy required to place an electron on a
gaseous atom, forming an anion.

X(g) + e 
 X (g) –

• Electron affinities may have positive or negative values.

• Negative values - energy released
• Positive values - energy absorbed

• Electron affinities increase (numerical value becomes more

negative) from left to right for a period and bottom to top for a
group.

• The greater (more negative) the electron affinity, the more

stable the anion will be.
74
Electron Affinity

• Graph of electron affinity (in kJ/mol) vs. atomic number for the
first 20 elements.
75
Modern Light Sources: LEDs and Lasers

• Light Emitting Diodes (LEDs) emit monochromatic light.

• Monochromatic light - light of a single wavelength or color.

• LEDs are solid-state devices.

• Simply a piece of solid material.

• Color emitted depends on identity of solid material.

76
Modern Light Sources: LEDs and Lasers

• LEDs
• Metallic leads connect to a piece of semiconductor material.
• Color emitted is determined by chemical composition of
semiconductor.
• Superior to incandescent lights in efficiency and durability.
77
Modern Light Sources: LEDs and Lasers

• Lasers emit monochromatic light; color of emitted light

depends on chemical composition of laser medium.

• Lasers emit coherent light; all light waves are perfectly in

phase and go through maxima and minima together.

78
Modern Light Sources: LEDs and Lasers

• Lasers - a direct result of the emergence of the quantum

mechanical model of the atom.
• An understanding of energy levels within the laser medium
is needed.
• Laser operation relies on stimulated emission, where the
electron population of higher energy level is greater than a
lower energy level.
• Emission occurs as electrons return to lower energy
states.

• “Population inversion” in lasers established by solids, liquids

or gases.
• Solid-state lasers are used in electronics.

79
Modern Light Sources: LEDs and Lasers

• Bright blue light emitted by an organic light emitting diode

(OLED).
• Holds promise of an entirely new class of paper-thin flexible
color displays.
80