CHEM 1600 Chapter 7

Chapter 7
Periodic Properties
of the Elements
© 2015 Pearson Education, Inc.

Arrangement of Electrons in Atoms
Electrons in atoms are arranged as
SHELLS (n)
SUBSHELLS (l)
ORBITALS (ml)

An electron configuration of an atom is a
particular distribution of electrons among
available subshells.
An orbital diagram of an atom shows how

the orbitals of a subshell are occupied by
electrons. Orbitals are represented with a
circle; electrons are represented with arrows
up for ms= +½ or down for ms= -½.

Pauli Exclusion Principle
• To make the quantum theory consistent with
experiment, Wolfgang Pauli stated :
• “No more than two electrons can occupy the

same orbital, and, if there are two electrons in
the same orbital, they must have opposite
spins.”
• This leads to the general statement that no two

electrons in an atom can have the same set of
four quantum numbers (n, l, ml, and ms).

Quantum Numbers
Electrons in an atom are arranged by: (quantum number)
Principle energy levels (shells) n
angular energy levels (sub-shells) l
oriented energy levels (orbitals) ml
Within an individual orbital, there may only be two electrons

differentiated by their spin.
Spin states (electrons) ms

The lowest-energy configuration of an atom
is called its ground state.
Any other allowed configuration represents

an excited state.
8|6
The Aufbau principle is a scheme used to
reproduce the ground-state electron
configurations by successively filling
subshells with electrons in a specific order
(the building-up order).
This order generally corresponds to filling

the orbitals from lowest to highest energy.
Note that these energies are the total
energy of the atom rather than the energy
of the subshells alone.
Subshell Filling Order

This results in the following order:
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p,
6s, 4f, 5d, 6p, 7s, 5f, 6d, 7p

Another way to learn the building-up order is
to correlate each subshell with a position on
the periodic table.
The principal quantum number, n, correlates
with the period number.
Groups IA and IIA correspond to the s
subshell; Groups IIIA through VIIIA
correspond to the p subshell; the “B” groups
correspond to the d subshell; and the bottom
two rows correspond to the f subshell. This
is shown on the next slide.
8 | 10
Orbital Filling of Electrons
Electrons fill orbitals from the bottom up: Aufbau

Orbital Filling of Electrons
Using the periodic table for electron configurations is easier

Orbital Filling:
The Aufbau Principle & Hund’s Rule
• Aufbau Principle:
• Lower energy orbitals fill first.
• Hund’s Rule:
• Degenerate orbitals (those of the same energy) are filled with

electrons until all are half filled before pairing up of electrons
can occur.
• Pauli exclusion principle:
• Individual orbitals only hold two electrons, and each should have
different spin.
“s” orbitals can hold 2 electrons

“p” orbitals can hold up to 6 electrons
“d” orbitals can hold up to 10 electrons
“f” orbitals can hold up to 14 electrons
Orbital Filling: The “Hund’s Rule”
Hund’s Rule.
Degenerate orbitals are filled with electrons
until all are half-filled before pairing up of
electrons can occur.
Consider a set of 2p orbitals:
  
2p
Electrons fill in this manner
Orbital Filling: The “Pauli Principle”
“Pauli exclusion principle”
Individual orbitals only hold two electrons, and
each should have opposite spin.
Consider a set of 2p orbitals:

 


 
2p  = spin up
*the convention  = spin down
is to write up,
then down. Electrons fill in this manner
Electron Configuration:
Orbital Box Notation
Electrons fill the orbitals from The electron configuration of an
lowest to highest energy. atom is the total sum of the
electrons from lowest to highest
Example: shell.
Nitrogen: N has an atomic number of 7, therefore 7 electrons
Orbitals
 
    
1s 2s 2p
Electron Configuration (spdf) notation: 1s2 2s2 2p3

More on Electron Configurations
• We use a numbering system to indicate
electrons in an atom
• Its given first by a number: 1,2,3,4, etc…
dictated by the period number electron shell
• Then follows a lower case letter: n,s,p,d, f…
dictated by the group from the periodic table
orbital type
• Then follows a superscript given over the letter:
indicates number of electrons in that orbital

Fluorine
Group 7A
3p Atomic number = 9
3s
9 total electrons
2p 1s2 2s2 2p5
2s
   
    
1s 1s 2s 2p
Neon
Group 8A
Atomic number = 10
10 total electrons
1s2 2s2 2p6
3p
3s     
    
2p 1s 2s 2p
2s Note that we have reached the
end of the 2nd period, and the 2nd
1s
shell is full!
Core of Noble Gas Notation
The electron configuration of an element can be represented as
a function of the core electrons in terms of a noble gas and the
valence electrons.
Full electron configuration spdf notation
For Silicon Si
1s22s22p63s23p2
Orbital Box Notation
[Ne]

  
3s 3p
spdf Notation
[Ne] 3s23s2
Transition Elements
Electron Configurations are written by shell even
though the electrons fill by the periodic table:
For Nickel Ni: last electron to fill: 3d8
electron configuration 1s2 2s2 2p6 3s2 3p6 4s2 3d8

by filling:
electron configuration
1s2 2s2 2p6 3s2 3p6 3d8 4s2
by shell:

Electron Configuration of Ions
• Write the electron configuration of the
neutral atom and the ion:
– Fe
– Fe2+

Electron Configurations of Ions
How do we know the configurations of ions?
By the magnetic properties of ions.

Ions with UNPAIRED ELECTRONS are
PARAMAGNETIC (attracted to a magnetic field).
Ions without UNPAIRED ELECTRONS are
DIAMAGNETIC (not attracted to a magnetic
field).
Fe3+ ions in Fe2O3 have 5

unpaired electrons.
This makes the sample
paramagnetic.

• Electron configurations that result in
unpaired electrons mean that the atom or ion
will have a net magnetic field; this is called
paramagnetism.
– Will be attracted to a magnetic field
• Electron configurations that result in all
paired electrons mean that the atom or ion
will have no magnetic field; this is called
diamagnetism.
– Slightly repelled by a magnetic field
Concept Check
• At your desk, give the configuration of the
following ions
– K+
– As3+

Development of the Periodic Table
Dmitri
Mendeleev and
Lothar Meyer
independently
came to the
same conclusion
about how
elements should
be grouped.
Periodic
Properties
of the
Elements
Mendeleev and the Periodic Table
Chemists mostly credit Mendeleev because he

also used chemical properties to organize the
table and predicted some missing elements and
Periodic
their expected properties, including germanium. Properties
of the
Elements
Atomic Number
• Mendeleev’s table was based on atomic
masses. It was the most fundamental
property of elements known at the time.
• About 35 years later, the nuclear atom was
discovered by Ernest Rutherford.
• Henry Moseley developed the concept of
atomic number experimentally. The number
of protons was considered the basis for the
periodic property of elements.
Periodic
Properties
of the
Elements
Periodicity
• Periodicity is the repetitive pattern of a property
for elements based on atomic number.
• The following properties are discussed in this
chapter:
– Sizes of atoms and ions
– Ionization energy
– Electron affinity
– Some group chemical property trends
• First, we will discuss a fundamental property
that leads to may of the trends, effective Periodic
nuclear charge. Properties
of the
Elements
Effective Nuclear Charge
• Many properties
depend on attractions
between valence
electrons and the
nucleus.
• Electrons are both
attracted to the
nucleus and repelled
by other electrons.
• The forces an electron
experiences depend
Periodic
on both factors. Properties
of the
Elements
 The effective nuclear charge, Zeff, is found this
way:
Zeff = Z − S
where Z is the atomic number and S is a
screening constant, usually close to the number of
inner electrons.
 Effective nuclear charge is a periodic property:
o It increases across a period.
o It decreases down a group.
Periodic
Properties
of the
Elements
Increases across a Period
Periodic
Properties
of the
Elements
What Is the Size of an Atom?
The nonbonding
atomic radius or
van der Waals
radius is half of the
shortest distance
separating two
nuclei during a
collision of atoms.
Periodic
Properties
of the
Elements
Sizes of Atoms
 The bonding atomic radius is half the
internuclear distance when atoms are bonded.
 The bonding atomic radius tends to
— decrease from left to right across a period (Zeff ↑).
— increase from top to bottom of a group (n ↑).
Periodic
Properties
of the
Elements
Sizes of Ions
• Determined by
interatomic distances
in ionic compounds
• Ionic size depends on
– the nuclear charge.
– the number of
electrons.
– the orbitals in which
electrons reside.
Periodic
Properties
of the
Elements
Sizes of Ions
• Cations are smaller than
their parent atoms:
– The outermost electron is
removed and repulsions
between electrons are
reduced.
• Anions are larger than
their parent atoms:
– Electrons are added and
repulsions between
electrons are increased.
Periodic
Properties
of the
Elements
Size of Ions—
Isoelectronic Series
• In an isoelectronic series, ions have the same
number of electrons.
• Ionic size decreases with an increasing nuclear
charge.
 An Isoelectronic Series (10 electrons)
• Note increasing nuclear charge with decreasing
ionic radius as atomic number increases
O2– F– Na+ Mg2+ Al3+

1.26 Å 1.19 Å 1.16 Å 0.86 Å 0.68 Å
Periodic
Properties
of the
Elements
Refer to a periodic table and arrange
the following elements in order of
increasing atomic radius: Br, Se, Te.
34 35 Te is larger than Se.

Se Br Se is larger than Br.
52
Te Br < Se < Te
Periodic
Properties
of the
Elements
8 | 39
Using the periodic table only, arrange the
following ions in order of increasing ionic
radius: Br-, Se2-, Sr2+.
34 35 These ions are
Se Br isoelectronic,
38 so their size decreases
Sr with increasing atomic
number:
Sr2+ < Br- < Se2-
Periodic
Properties
of the
Elements
9 | 40
Ionization Energy (I)
• The ionization energy is the minimum
energy required to remove an electron from
the ground state of a gaseous atom or ion.
– The first ionization energy is that energy
required to remove the first electron.
– The second ionization energy is that energy
required to remove the second electron, etc.
• Note: the higher the ionization energy, the
more difficult it is to remove an electron!
Periodic
Properties
of the
Elements
Ionization Energy
• It requires more energy to remove each successive
electron.
• When all valence electrons have been removed, it
takes a great deal more energy to remove the next
electron.
Periodic
Properties
of the
Elements
Periodic Trends in
First Ionization Energy (I1)
1) I1 generally increases across a period.
2) I1 generally decreases down a group.
3) The s- and p-block elements show a larger
range of values for I1. (The d-block
generally increases slowly across the
period; the f-block elements show only
small variations.)
Periodic
Properties
of the
Elements
Factors that Influence
Ionization Energy
 Smaller atoms have higher I values.
 I values depend on effective nuclear charge
and average distance of the electron from the
nucleus.
Periodic
Properties
of the
Elements
Irregularities in the General Trend
• The trend is not followed when the added
valence electron in the next element
 enters a new sublevel (higher energy sublevel);
 is the first electron to pair in one orbital of the
sublevel (electron repulsions lower energy).
Periodic
Properties
of the
Elements
• Cations: The electrons are lost from the
highest energy level (n value).
 Li+ is 1s2 (losing a 2s electron).
 Fe2+ is 1s22s22p63s23p63d6 (losing two
4s electrons).
• Anions: The electron configurations are
filled to ns2np6; e.g., F– is 1s22s22p6
(gaining one electron in 2p).
Periodic
Properties
of the
Elements
Electron Affinity
 Electron affinity is the energy change
accompanying the addition of an electron to a
gaseous atom:
Cl + e−  Cl−
 It is typically exothermic, so, for most

elements, it is negative!
Periodic
Properties
of the
Elements
General Trend in Electron Affinity
 Not much change in a group.
 Across a period, it generally
increases. Three notable
exceptions include the
following:
1) Group 2A: s sublevel is full!
2) Group 5A: p sublevel is
half-full!
3) Group 8A: p sublevel is full!
Note: the electron affinity
for many of these elements Periodic
Properties
is positive (X– is unstable). of the
Elements
Refer to a periodic table and arrange
the following elements in order of
increasing ionization energy: As, Br,
Sb.
33 35 Sb is larger than As.

As Br As is larger than Br.
51
Sb Ionization energies:
Sb < As < Br
Periodic
Properties
of the
Elements
8 | 49
Concept Check 8.3
Given the following information for element E, identify the
element’s group in the periodic table: The electron affinity
of E is negative (that is, it does not form a stable negative
ion). The first ionization energy of E is less than the
second ionization energy, which in turn is very much less
than its third ionization energy.
The electron affinity is > 0, so the element must be in
Group IIA or VIIIA.
The dramatic difference in ionization energies is at the

third ionization.
The element is in Group IIA. Periodic
Properties
of the
Elements
8 | 50
Metal, Nonmetals, and Metalloids
Periodic
Properties
of the
Elements
Metals Differ from Nonmetals
• Metals tend to form cations.
• Nonmetals tend to form anions.
Periodic
Properties
of the
Elements
Metals
 Most of the elements in nature are metals.
 Properties of metals:
Shiny luster
Conduct heat and electricity
Malleable and ductile
Solids at room temperature (except mercury)
Low ionization energies/form cations easily
Periodic
Properties
of the
Elements
Metal Chemistry
• Compounds formed between metals and
nonmetals tend to be ionic.
• Metal oxides tend to be basic.
Periodic
Properties
of the
Elements
Nonmetals
• Nonmetals are found on the right hand side of the
periodic table.
• Properties of nonmetals include the following:
• Solid, liquid, or gas (depends on element)
• Solids are dull, brittle, poor conductors
• Large negative electronegativity/form anions
readily
Periodic
Properties
of the
Elements
Nonmetal Chemistry
• Substances containing only nonmetals are

molecular compounds.
• Most nonmetal oxides are acidic. Periodic
Properties
of the
Elements
Recap of a Comparison of the
Properties of Metals and Nonmetals
Periodic
Properties
of the
Elements
Metalloids
• Metalloids have some characteristics of metals
and some of nonmetals.
• Several metalloids are electrical semiconductors
(computer chips).
Periodic
Properties
of the
Elements
Group Trends
• Elements in a group have similar properties.
• Trends also exist within groups.
• Groups Compared:
 Group 1A: The Alkali Metals
 Group 2A: The Alkaline Earth Metals
 Group 6A: The Oxygen Group
 Group 7A: The Halogens
 Group 8A: The Noble Gases
Periodic
Properties
of the
Elements
Alkali Metals
• Alkali metals are soft,
metallic solids.
• They are found only in
compounds in nature,
not in their elemental
forms.
• Typical metallic
properties (luster,
conductivity) are seen
in them.
Periodic
Properties
of the
Elements
Alkali Metal Properties
• They have low densities and melting points.
• They also have low ionization energies.
Periodic
Properties
of the
Elements
Alkali Metal Chemistry
Their reactions with water are famously exothermic.

Periodic
Properties
of the
Elements
Differences in Alkali
Metal Chemistry
• Lithium reacts with oxygen to make an oxide:
4 Li + O2  2 Li2O
• Sodium reacts with oxygen to form a peroxide:
2 Na + O2  Na2O2
• K, Rb, and Cs also form superoxides:
M + O2  MO2
Periodic
Properties
of the
Elements
Flame Tests
• Qualitative tests for alkali metals include
their characteristic colors in flames.
Periodic
Properties
of the
Elements
Alkaline Earth Metals—Compare to
Alkali Metals
• Alkaline earth metals have higher densities

and melting points than alkali metals.
• Their ionization energies are low, but not as
Periodic
low as those of alkali metals. Properties
of the
Elements
Alkaline Earth Metals
• Beryllium does not
react with water, and
magnesium reacts only
with steam, but the
other alkaline earth
metals react readily
with water.
• Reactivity tends to
increase as you go
down the group.
Periodic
Properties
of the
Elements
Group 6A—Increasing in Metallic
Character down the Group
• Oxygen, sulfur, and selenium are nonmetals.

• Tellurium is a metalloid.
• The radioactive polonium is a metal. Periodic
Properties
of the
Elements
Group 7A—Halogens
• The halogens are typical nonmetals.

• They have highly negative electron affinities, so
they exist as anions in nature.
• They react directly with metals to form metal Periodic
Properties
halides. of the
Elements
Group 8A—Noble Gases
• The noble gases have very large ionization energies.

• Their electron affinities are positive (can’t form stable
anions).
• Therefore, they are relatively unreactive. Periodic
Properties
• They are found as monatomic gases. of the
Elements

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CHEM 1600 Chapter 7

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Chapter 7

© 2015 Pearson Education, Inc.

Electrons in atoms are arranged as

© 2015 Pearson Education, Inc.

An orbital diagram of an atom shows how

© 2015 Pearson Education, Inc.

• “No more than two electrons can occupy the

• This leads to the general statement that no two

© 2015 Pearson Education, Inc.

Principle energy levels (shells) n

angular energy levels (sub-shells) l

oriented energy levels (orbitals) ml

Within an individual orbital, there may only be two electrons

Spin states (electrons) ms

© 2015 Pearson Education, Inc.

Any other allowed configuration represents

This order generally corresponds to filling

© 2015 Pearson Education, Inc.

© 2015 Pearson Education, Inc.

Electrons fill orbitals from the bottom up: Aufbau

Using the periodic table for electron configurations is easier

• Degenerate orbitals (those of the same energy) are filled with

“s” orbitals can hold 2 electrons

Consider a set of 2p orbitals:

Nitrogen: N has an atomic number of 7, therefore 7 electrons

Electron Configuration (spdf) notation: 1s2 2s2 2p3

© 2015 Pearson Education, Inc.

Orbital Box Notation

For Nickel Ni: last electron to fill: 3d8

electron configuration 1s2 2s2 2p6 3s2 3p6 4s2 3d8

© 2015 Pearson Education, Inc.

© 2015 Pearson Education, Inc.

By the magnetic properties of ions.

Fe3+ ions in Fe2O3 have 5

© 2015 Pearson Education, Inc.

© 2015 Pearson Education, Inc.

Chemists mostly credit Mendeleev because he

O2– F– Na+ Mg2+ Al3+

34 35 Te is larger than Se.

 It is typically exothermic, so, for most

33 35 Sb is larger than As.

The dramatic difference in ionization energies is at the

• Substances containing only nonmetals are

Their reactions with water are famously exothermic.

• Alkaline earth metals have higher densities

• Oxygen, sulfur, and selenium are nonmetals.

• The halogens are typical nonmetals.

• The noble gases have very large ionization energies.

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