Lecture 03

Lecture Presentation
Chapter 3
Periodic
Properties of the
Elements
Catherine E. MacGowan
Armstrong State University
© 2018 Pearson Education, Inc.
Elemental Patterns: The Periodic Law of
Elemental Properties
• Reoccurring patterns in the physical and chemical
properties of elements aid scientists in predicting
undiscovered elements and understanding elemental
behavior.
• Example: aluminum (Al) vs. indium (In)
– Aluminum’s density is low, 2.70 g/cm3, when compared to
indium’s density, 7.31 g/cm3.
– The density of elements tends to increase as you move
down a column of elements.
• The mass-to-volume ratio of atoms increases as you move
down a column of elements.
– Density, along with other properties such as atomic radii, is a
periodic property of matter.
• To be periodic means to exhibit a repeating pattern.
Elemental Patterns: The Periodic Law of
Elemental Properties

Finding Elemental Patterns: The Periodic
Law and the Periodic Table
• During the nineteenth century scientists

began to notice that certain groups of
elements had similar properties.
• Recurring patterns in physical and chemical

properties were observed when elements
were arranged in order of increasing mass.

The Periodic Law
• Mendeleev (1869) summarized these

observations in the periodic law:
– When the elements are arranged in order of
increasing mass, certain sets of properties recur
periodically.

Mendeleev’s Periodic Table: Making Sense
of Patterns
• Mendeleev’s periodic table organized known
elements of the time in a table format.
– He arranged the rows so that elements with similar
properties would fall within the same vertical columns.
– Several of his columns contained gaps, which allowed him
to predict the existence and even the properties of yet
undiscovered elements.
• Mendeleev predicted the existence of an element he called
eka-silicon.

The Modern Periodic Table: Its Format
• The elements are listed in order of increasing atomic number
rather than increasing relative mass as they were in
Mendeleev’s periodic table.
• Rows of the table are referred to as periods.

• Columns in the table are referred to as groups or a family.
– Elements in a group or family have similar properties.
– NOTE: Mendeleev’s periodic law predicts patterns but does NOT
explain why the patterns or similarity in properties occurs.
• Quantum theory explains the why.
The Modern Periodic Table: Groupings
• Elements in the periodic table are classified as the
following:
– Metals
– Nonmetals
– Metalloids
• The periodic table can also be divided into
– main-group elements, whose properties tend to be largely
predictable based on their position in the periodic table.
• In the periodic table this area is labeled by a number and the
letter A.
– transition elements and inner transition metals or transition
metals, whose properties tend to be less predictable based
simply on their position in the periodic table.
• In the periodic table this area is labeled by a number and the
letter B.
Modern Periodic Table

Electron Configuration: How an Atom’s
Electrons Occupy Orbitals
• Quantum-mechanical theory describes the

behavior of electrons in atoms.
• Electrons in atoms exist in orbitals.
• A description of the orbitals occupied by
electrons is called an electron configuration.

Electron Configuration and Quantum Theory
Connection: How Electrons Are Arranged Around the
Atom’s Nucleus
• The solution resulting from Schrödinger’s equation for the
hydrogen atom showed that its one electron will occupy the
lowest energy orbital in the atom.
• However, for multi-electron atoms (all others but the H atom),

the equation cannot be exactly solved because of the
electron–electron interactions that happen between two
electrons.
– However, approximate solutions showed the orbitals to be
hydrogen-like.
• Two additional concepts affect multi-electron atoms: electron
spin (ms quantum number) and energy splitting of sublevels.
Electron Spin (ms)
• Spin is a fundamental property of all electrons.

– All electrons have the same amount of spin.
• The orientation of the electron spin is quantized.
– Meaning it can be only in one direction or its opposite.
– Electrons in an atomic orbital can spin up or spin down.
• The electron’s spin adds a fourth quantum number to the

description of electrons in an atom, called the spin
quantum number, ms.
Electron Spin (ms) and the Pauli Exclusion
Principle
• Electron spin, ms, is given values of +½ or −½.
• Orbital diagrams use a square to represent each orbital and
a half-arrow to represent each electron in the orbital.
– By convention,
• a half-arrow pointing up is used to represent an electron in an orbital
with spin up.
• a half-arrow pointing down is used to represent an electron in an
orbital with spin down.
• Spins must cancel in an orbital.
– Paired, meaning the two electrons in an orbital must have
opposite spins (i.e., one with the magnetic field; the other against
the magnetic field).
• Paired spins are diamagnetic.
The Pauli Exclusion Principle
• No two electrons in an atom may have the same set

of four quantum numbers.
• Therefore, no orbital may have more than two
electrons, and the electrons must have opposite
spins.
Example: Helium (He)

Sublevel Energy Splitting in Multi-electron
Atoms
• The sublevels (orbital quantum # l : s, p, d, f, etc.) in each
principal energy shell of hydrogen, or other single electron
systems, all have the same energy.
• Orbitals with the same energy (E) are said to be degenerate.
• For multi-electron atoms, the energies of the sublevels are
split.
– Caused by charge interaction, shielding, and penetration
• The lower the value of the l quantum number (orbital
quantum number), the less energy the sublevel has.
E (s orbital (l = 0)) < E (p orbital (l = 1)) < E (d orbital (l = 2)) < E (f orbital (l = 3))

General Energy Ordering of Orbitals for
Multi-electron Atoms
• Electrons enter
(e.g., fill) atomic
orbitals from
lowest energy to
highest: aufbau
principle.

Coulomb’s Law: Attractive and Repulsive
Forces between Electrons
• Coulomb’s law describes the attractions and repulsions
between charged particles.
– For like charges, the potential energy (E) is positive and
decreases as the particles get farther apart as r increases.
– For opposite charges, the potential energy is negative and
becomes more negative as the particles get closer together.
– The strength of the interaction increases as the size of the
charges increases.
• Electrons are more strongly attracted to a nucleus with a 2+
charge than to a nucleus with a 1+ charge.

Shielding and Effective Nuclear Charge (Zeff)
• In a multi-electron atom, each electron experiences
both an attraction to the protons in the nucleus and
the repulsion by other electrons in the atom.
• These repulsions cause an electron to experience
a net reduction in attraction to the nucleus.
– We refer to this as shielding: The electron is shielded
from the nucleus.
• The electron does not experience the full attraction by protons in
the nucleus because the other electrons in the atom are
interfering/blocking the attractive forces.
• The total amount of attraction that an electron feels
for the nucleus’s protons is called the effective
nuclear charge (Zeff) of the electron.
Shielding and Penetration
• The closer an electron is to the nucleus, the more attraction
the electron experiences from the nucleus protons.
• Attraction between nucleus protons and orbiting electrons is
related to the orbital type the electron occupies.
– Example: Electrons in the s orbital are better
shielders/screeners than electrons in p orbitals.
• s>p>d>f
• The degree of penetration is related to the orbital’s radial
distribution function.

Electron Spatial Distribution and Sublevel
Splitting as it Relates to Degree of Penetration
• The radial distribution function
shows that the 2s orbital penetrates
more deeply into the 1s orbital than
does the 2p.
• The weaker penetration of the 2p
sublevel means that electrons in the
2p sublevel experience more
repulsive force; they are more
shielded from the attractive force of
the nucleus.
• The deeper penetration of the 2s
electrons means electrons in the 2s
sublevel experience a greater
attractive force to the nucleus and
are not shielded as effectively.
Shielding and Penetration
• Penetration causes the energies of sublevels in the same
principal level to not be degenerate.
• In the fourth and fifth principal levels, the effects of
penetration become so important that the s orbital lies lower
in energy than the d orbitals of the previous principal level.
• The energy separations between one set of orbitals and the
next become smaller beyond the 4s orbital.
– The ordering can therefore vary among elements, causing
variations in the electron configurations of the transition metals
and their ions.

Question about Shielding and Penetration
Which statement is true?
(a) An orbital that penetrates into the region occupied by core
electrons is more shielded from nuclear charge than an orbital
that does not penetrate and therefore has a higher energy.
(b) An orbital that penetrates into the region occupied by core
electrons is less shielded from nuclear charge than an orbital
that does not penetrate and therefore has a higher energy.
(c) An orbital that penetrates into the region occupied by core
electrons is less shielded from nuclear charge than an orbital
that does not penetrate and therefore has a lower energy.
(d) An orbital that penetrates into the region occupied by core
electrons is more shielded from nuclear charge than an orbital
that does not penetrate and therefore has a lower energy.

Electron Configuration for Multi-electron
Atoms
• Energy levels and sublevels fill from lowest energy to
highest:
– s→p→d→f
– This is known as the aufbau principle.
• Orbitals that are in the same sublevel have the same

energy (i.e., degenerate).
– Example: E(px) = E(py) = E(pz)
• There can be no more than two electrons per orbital.
– This is known as the Pauli exclusion principle.

Electron Configuration for Multi-electron
Atoms
Hund’s Rule:
• When filling orbitals that have the same
energy (degenerate), place one electron in
each orbital before completing pairs.

Summarizing the Filling of Electrons in Atomic Orbitals
• Electrons occupy orbitals so as to minimize the energy of
the atom; therefore, lower-energy orbitals fill before higher-
energy orbitals.
– Orbitals fill in the following order:
• 1s 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s 4f 5d 6p
• Orbitals can hold no more than two electrons each. When
two electrons occupy the same orbital, their spins are
opposite.
– This is another way of expressing the Pauli exclusion principle (no
two electrons in one atom can have the same four quantum
numbers).
• When orbitals of identical energy are available, electrons
first occupy these orbitals singly with parallel spins rather
than in pairs (Hund’s rule).
– Once the orbitals of equal energy are half-full, the electrons start
to pair.
Problem Solving: Electron Configuration
Write the following electron configurations:
a. Ca a. Ca: 1s22s22p63s23p64s2 or [Ar]4s2
b. Fe b. Fe: 1s22s22p63s23p64s23d6 or [Ar]4s23d6
c. I c. I: 1s22s22p63s23p64s23d104p65s24d105p5
or [Kr] 5s24d105p5
d. Pb d. Pb:
1s22s22p63s23p64s23d104p65s24d105p66s24f145d106p2
or [Xe] 6s24f145d106p2

Problem Solving: Orbital Writing
Example 3.2 Writing Orbital Diagrams
Write the orbital diagram for sulfur and determine its number of unpaired electrons.
Solution
Sulfur’s atomic number is 16, so it has 16 electrons and the electron configuration 1s2 2s2 2p6 3s2 3p4. Draw a box
for each orbital, putting the lowest energy orbital (1s) on the far left and proceeding to orbitals of higher energy to
the right.
Distribute the 16 electrons into the boxes representing the orbitals, allowing a maximum of two electrons per orbital
and obeying Hund’s rule. You can see from the diagram that sulfur has two unpaired electrons.
Two unpaired electrons
For Practice 3.2

Write the orbital diagram for Ar and determine its number of unpaired electrons.

Electron Configuration, Valence Electrons,
and the Periodic Table
• Electrons in lower-energy shells are called core (inner)
electrons.
• The electrons in all the sublevels with the highest principal energy
shell (level) are called the valence electrons.
– The valence electrons are located in the outermost shell (energy level).
• One of the most important factors in the way an atom behaves,

both chemically and physically, is the number of valence
electrons.
– It is the valance electrons that participate in bonding and are lost to make
cations.
– The valance shell is where electrons are added to make anions.
Problem Solving: Core and Valence Electrons
Example 3.3 Valence Electrons and Core Electrons
Write the electron configuration for Ge. Identify the valence electrons and the core electrons.
Solution
To write the electron configuration for Ge, determine the total number of electrons from germanium’s atomic number
(32) and distribute them into the appropriate orbitals.
Ge 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p2
Because germanium is a main-group element, its valence electrons are those in the outermost principal energy level.
For germanium, the n = 1, 2, and 3 principal levels are complete (or full), and the n = 4 principal level is outermost.
Consequently, the n = 4 electrons are valence electrons and the rest are core electrons.
Note: In this book, we always write electron configurations with the orbitals in the order of filling. However, it is
also common to write electron configurations in the order of increasing principal quantum number. The electron
configuration of germanium written in order of increasing principal quantum number is:
Ge 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p2
For Practice 3.3

Write the electron configuration for phosphorus. Identify its valence electrons and core electrons.

Orbital Blocks and Their Position in the Periodic Table
Summarizing Periodic Table Organization
• The periodic table is divisible into four blocks corresponding to
the filling of the four quantum sublevels (s, p, d, and f ).
• The group number of a main-group element is equal to the
number of valence electrons for that element.
• The row number of a main-group element is equal to the highest
principal quantum number of that element.

Orbital Blocks and Their Position in the
Periodic Table
Example 3.4 Writing Electron Configurations from the Periodic Table
Refer to the periodic table to write the electron configuration for selenium (Se).
Solution
The atomic number of Se is 34. The noble gas that precedes Se in the periodic table is argon, so the inner electron
configuration is [Ar]. Obtain the outer electron configuration by tracing the elements between Ar and Se and
assigning electrons to the appropriate orbitals. Begin with [Ar]. Because Se is in row 4, add two 4s electrons as you
trace across the s block (n = row number). Next, add ten 3d electrons as you trace across the d block
(n = row number – 1). (See explanation after example.) Lastly, add four 4p electrons as you trace across the p block
to Se, which is in the fourth column of the p block (n = row number).
Se [Ar] 4s2 3d10 4p4

Orbital Blocks and Their Position in the
Periodic Table
Example 3.4 Writing Electron Configurations from the Periodic Table
Continued
For Practice 3.4

Refer to the periodic table to write the electron configuration of bismuth (Bi).
For More Practice 3.4

Refer to the periodic table to write the electron configuration for iodine (I).

Transition and Inner Transition Metals
• Transition metals (d block) and inner transition metals
(f block) exhibit trends differing from those of main-group
elements (s block and p block).
– Because of sublevel splitting, the 4s sublevel is lower in energy than
the 3d sublevel; therefore, the 4s orbital fills before the 3d orbital.
• The difference in energy is not large.
• Some transition metals have irregular electron configurations
(anomalies) in which the ns only partially fills before the (n − 1)d
or doesn’t fill at all.
– Examples: Cr, Mo, Cu, Ag
• Note these anomalies happen when an s electron jumps to a d orbital to
create a half-filled (e.g., Cr & Mo) or completely filled (e.g., Cu & Ag)
sublevel.
• Therefore, their electron configurations must be found experimentally.

Examples of Transition and Inner Transition
Metals’ Electron Configurations
Expected Found Experimentally
• Cr = [Ar]4s23d4 • Cr = [Ar]4s13d5
• Cu = [Ar]4s23d9 • Cu = [Ar]4s13d10
• Mo = [Kr]5s24d4 • Mo = [Kr]5s14d5
• Ru = [Kr]5s24d6 • Ru = [Kr]5s14d7
• Pd = [Kr]5s24d8 • Pd = [Kr]5s04d10

Electron Configuration and Elemental
Properties
• The properties of the
elements follow a periodic
pattern.
– Elements in the same column
have similar properties.
– The elements in a period
show a pattern that repeats.
• The quantum-mechanical
model explains this
because the number of
valence electrons and the
types of orbitals they
occupy are also periodic.
Properties: Noble Gases
• The noble gases have eight
valence electrons.
– Except for He, which has only two
electrons
• They are especially nonreactive.
– He and Ne are practically inert.
• The reason the noble gases are so
nonreactive is that the electron
configuration of the noble gases is
especially stable.
– They have the full shell look.

Properties: The Metals
• Metallic elements make up the majority of the elements in
the periodic table.
– Alkali Metals:
• They have one more electron than the previous noble gas and
occupy the first column.
• In their reactions, the alkali metals lose one electron, and
the resulting electron configuration is the same as that of a
noble gas.
– Forming a cation with a 1+ charge
– Alkaline Earth Metals:
• They have two more electrons than the previous noble gas and
occupy the second column.
• In their reactions, the alkaline earth metals lose two electrons,
and the resulting electron configuration is the same as that of a
noble gas.
– Forming a cation with a 2+ charge
Properties: The Metals
• Metallic elements make up the majority of the
elements in the periodic table.
– Transition and Inner Transition Metals:
• They are located in the d-block area of the periodic
table.
• In chemical reactions, they will lose electron(s) from s
and then d orbitals to form cations.
– p-block Metals:
• They are located in the p-block area (left-hand side of
the metalloids) of the periodic table.
• In chemical reactions, they will lose electrons from the
s and p orbitals to form cations.
Metallic Behavior and Electron Configuration

Behavior and Electron Configuration of
Metalloids and Nonmetals
Metalloids:
• They are located in the p-block area of the periodic
table between the metal and nonmetal elements.
– Sitting on the “steps” of the zigzag diagonal line indicated
on the periodic table
• Metalloids in chemical reactions can exhibit metallic
or nonmetallic behaviors.
• Metalloids can either lose electron(s) from p and
then s orbitals to form cations or gain electrons in
their p orbitals to form anions.

Behavior and Electron Configuration of
Metalloids and Nonmetals
Nonmetals:
• They are located in the upper right-hand side of the
periodic table.
– p-block area
• In chemical reactions nonmetal elements will gain
electrons in the p orbitals, resulting in their ions
having the same electron configuration as a noble
gas at the end of their period (row).
• Nonmetals form anions.

Properties
Halogens:
• They are nonmetals.
• They have one fewer electron than the next
noble gas.
• In their reactions with metals, the halogens
tend to gain an electron and attain the
electron configuration of the next noble gas,
forming an anion with charge 1−.
• In their reactions with nonmetals, they tend to
share electrons with the other nonmetal so
that each attains the electron configuration of
a noble gas.

Electron Configuration and Ion Formation
• Ion formation can be predicted by an element’s location in
the periodic table.
• These atoms form ions that will result in an electron
configuration that is the same as that of the nearest
noble gas.
• Metals form cations (positively charged atoms).
– Alkali metals (group 1A) form only 1+ cations.
– Alkaline earth metals (group 2A) form only 2+ cations.
– Transition, inner transition, and p-block metals form a variety
of charged cations.
• Nonmetals form anions (negatively charged atoms).
– Halogens (group 7A) usually gain one electron to form
1– anions.
– Other nonmetals can form a variety of charged anions.

Electron Configuration and Ion Formation

Problem Solving: Predicting Ionic Charge
Example 3.5 Predicting the Charge of Ions
Predict the charges of the monoatomic (single atom) ions formed by each main-group element.
a. Al b. S
Solution
a. Aluminum is a main-group metal and tends to lose electrons to form a cation with the same electron
configuration as the nearest noble gas. The electron configuration of aluminum is 1s2 2s2 2p6 3s2 3p1. The
nearest noble gas is neon, which has an electron configuration of 1s2 2s2 2p6. Therefore, aluminum loses three
electrons to form the cation Al3+.
b. Sulfur is a nonmetal and tends to gain electrons to form an anion with the same electron configuration as the
nearest noble gas. The electron configuration of sulfur is 1s2 2s2 2p6 3s2 3p4. The nearest noble gas is argon,
which has an electron configuration of 1s22s2 2p6 3s2 3p6. Therefore, sulfur gains two electrons to form the
anion S2−.
For Practice 3.5

Predict the charges of the monoatomic ions formed by each main-group element.
a. N b. Rb

Effective Nuclear Charge and Periodic Trends
• The effective nuclear charge is a net positive charge that is
attracting a particular electron.
– Core electrons efficiently shield electrons in the outermost principal
energy level from nuclear charge.
– Outermost electrons in the valence shell do not efficiently shield one
another from nuclear charge.
• Periodic Trend: Effective nuclear charge INCREASES as you
go across a period and DECREASES as you descend down a
column.
– Electrons in the same energy level contribute to screening, but since
their contribution is so small, they are not part of the calculation.
– For example: Electrons in s orbitals are better shielders than electrons
in p orbitals.
• s>p>d>f
– As you go across a period you are adding electrons in the same
energy level but in different orbitals, whose shielding ability decreases.

Effective Nuclear Charge and Periodic Trends
• Z is the nuclear charge, and S is the number of
electrons in lower energy levels.
– Electrons in the same energy level contribute to screening,
but since their contribution is so small, they are not part of
the calculation.
– Trend is s > p > d > f.
Zeffective = Z − S

Effective Nuclear Charge and the Screening
Effect
Which atom’s valence electrons experience the greatest

effective nuclear charge?
(a) the valence electrons in Mg
(b) the valence electrons in Al
(c) the valence electrons in S

Periodic Trends: Atomic Radii
• There are several methods for measuring the radius of
an atom, and they give slightly different numbers.
– Van der Waals radius = nonbonding
– Covalent radius = bonding radius
– Atomic radius is an average radius of an atom based on
measuring large numbers of elements and compounds.

Periodic Trends: Atomic Radii and Effective
Nuclear Charge
• Atomic radius decreases across a period (left to right).
– Adding electrons to the same valence shell
– Effective nuclear charge increases across a period.
– Valence shell held closer
• Atomic radius increases down a group.
– Valence shell farther
distance from nucleus
– Effective nuclear charge
decreases as you go
down a column.

Summarizing Atomic Radii Trend for
Main-Group Elements
• The size of an atom is related to the distance
the valence electrons are from the nucleus.
– The larger the orbital an electron is in, the farther its
most probable distance will be from the nucleus, and
the less attraction it will have for the nucleus.
– Traversing down a group adds a principal energy
level, and the larger the principal energy level an
orbital is in, the larger its volume.
– Quantum mechanics predicts that the atoms should
get larger down a column.

Main-Group Elements
• The larger the effective nuclear charge an
electron experiences, the stronger the
attraction it will have for the nucleus.
– The stronger the attraction the valence electrons
have for the nucleus, the closer their average
distance will be to the nucleus.
– Traversing across a period increases the effective
nuclear charge on the valence electrons.
– Quantum mechanics predicts that the atoms should
get smaller across a period.

Transition Elements
• Atoms in the same group increase in size down the
column.
• Atomic radii of transition metals are roughly the
same size across the d block.
– Much less difference than across main-group
elements
– Valence shell ns2, not the (n − 1)d electrons
– Effective nuclear charge on the ns2 electrons
approximately the same

Problem Solving: Predicting Atomic Radii
Example 3.6 Atomic Size
On the basis of periodic trends, choose the larger atom in each pair (if possible). Explain your choices.
a. N or F b. C or Ge c. N or Al d. Al or Ge
Solution
a. N atoms are larger than F atoms
because, as you trace the path between
N and F on the periodic table, you
move to the right within the same
period. As you move to the right
across a period, the effective nuclear
charge experienced by the outermost
electrons increases, resulting in a
smaller radius.
b. Ge atoms are larger than C atoms

C and Ge on the periodic table, you
move down a column. Atomic size
increases as you move down a column
because the outermost electrons
occupy orbitals with a higher principal
quantum number that are therefore
larger, resulting in a larger atom.

Continued
c. Al atoms are larger than N atoms

N and Al on the periodic table, you
move down a column (atomic size
increases) and then to the left across a
period (atomic size increases). These
effects add together for an overall
increase.
d. Based on periodic trends alone, you

cannot tell which atom is larger,
because as you trace the path between
Al and Ge you go to the right across a
period (atomic size decreases) and
then down a column (atomic size
increases). These effects tend to
counter each other, and it is not easy
to tell which will predominate.

Continued
For Practice 3.6

On the basis of periodic trends, choose the larger atom in each pair (if possible):
a. Sn or I b. Ge or Po c. Cr or W d. F or Se

Arrange the elements in order of decreasing radius: S, Ca, F, Rb, Si.

Ion: Magnetic Properties
• 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

Problem Solving: Electronic Configuration and Magnetism
Example 3.7 Electron Configurations and Magnetic Properties

for Ions
Write the electron configuration and orbital diagram for each ion and determine whether each is diamagnetic or
paramagnetic.
a. Al3+ b. S2− c. Fe3+
Solution
a. Al3+
Begin by writing the electron configuration of the neutral Al [Ne] 3s2 3p1
atom.
Since this ion has a 3+ charge, remove three electrons to Al3+ [Ne] or [He] 2s2 2p6
write the electron configuration of the ion. Write the orbital
diagram by drawing half-arrows to represent each electron Al3+ [He]
in boxes representing the orbitals. Because there are no
unpaired electrons, Al3+ is diamagnetic. Diamagnetic
b. S2−
Begin by writing the electron configuration of the neutral S [Ne] 3s2 3p4
atom.
Since this ion has a 2− charge, add two electrons to write S2– [Ne] 3s2 3p6
the electron configuration of the ion. Write the orbital
diagram by drawing half-arrows to represent each electron S2– [Ne]
in boxes representing the orbitals. Because there are no
unpaired electrons, S2− is diamagnetic. Diamagnetic

Problem Solving: Electronic Configuration and Magnetism
Example 3.7 Electron Configurations and Magnetic Properties

for Ions
Continued
c. Fe3+
Begin by writing the electron configuration of the neutral Fe [Ar] 4s2 3d6
atom.
Since this ion has a 3+ charge, remove three electrons to Fe3+ [Ar] 4s0 3d5
write the electron configuration of the ion. Since it is a
transition metal, remove the electrons from the 4s orbital Fe3+ [Ar]
before removing electrons from the 3d orbitals. Write the
orbital diagram by drawing half-arrows to represent each
electron in boxes representing the orbitals. There are
unpaired electrons, so Fe3+ is paramagnetic. Paramagnetic
For Practice 3.7

Write the electron configuration and orbital diagram for each ion and predict whether each will be paramagnetic
or diamagnetic.
a. Co2+ b. N3− c. Ca2+

Radii of Atoms and Their Ions: Cations
• Cation radius is smaller than
its corresponding atom radius.
– The loss of electrons results in
the remaining electrons in the
atom experiencing a larger
effective nuclear charge
than the neutral atom.
• Traversing down a group
increases the (n − 1) level,
causing the cations to get
larger.
• Traversing to the right across
a period increases the
effective nuclear charge for
isoelectronic cations, causing
the cations to get smaller.
Radii of Atoms and Their Ions: Anions
• When atoms form anions, electrons
are added to the valence shell.
• These “new valence electrons”
experience a smaller effective
nuclear charge than the “old
valence electrons.”
• The result is that the anion is larger
than the atom. Traversing down a
group increases the n level, causing
the anions to get larger.
• Traversing to the right across a
period increases the effective
nuclear charge for isoelectronic
anions, causing the anions to get
smaller.

Ions: Ionic Radii Summary
• Ions in the same group have the same charge.
• Ion size increases down the column.
– Higher valence shell, larger
• Cations are smaller than neutral atoms; anions are
larger than neutral atoms.
• Cations are smaller than anions.
– Except Rb+ and Cs+, which are bigger than or the same size
as F− and O2−.
• Larger positive charge = smaller cation
– For isoelectronic species
– Isoelectronic = same electron configuration
• Larger negative charge = larger anion
– For isoelectronic species
Problem Solving: Ion Size
Example 3.8 Ion Size
Choose the larger atom or ion from each pair.
a. S or S2− b. Ca or Ca2+ c. Br− or Kr
Solution
a. The S2− ion is larger than an S atom because the S2− ion has the same number of protons as S but two more
electrons. The additional electron–electron repulsions cause the anion to be larger than the neutral atom.
b. A Ca atom is larger than a Ca2+ ion because the Ca atom has an argon core and two 4s electrons. Because the
4s electrons are the outermost electrons and they are shielded from the nuclear charge by the core electrons,
they contribute greatly to the size of the Ca atom. The Ca2+ cation, having lost the outermost 4s electrons, has
only the argon core and carries a charge of 2+, which makes it smaller than the Ca atom.
c. A Br− ion is larger than a Kr atom because, although they are isoelectronic, Br− has one fewer proton than Kr,
resulting in a smaller pull on the electrons and therefore a larger radius.
For Practice 3.8

Choose the larger atom or ion from each pair.
a. K or K+
b. F or F−
c. Ca2+ or Cl−

Periodic Trend: Ionization Energy (Potential)
Ionization Energy (IE):
• It is the minimum energy needed to remove an electron
from an atom or ion in the gas phase.
• It is an endothermic process (requires the input of energy
to remove the electron).
– Valence electron easiest to remove, lowest IE
• First ionization energy = energy to remove electron from
neutral atom
– All atoms have first ionization energy.
M(g) + IE1 → M1+(g) + 1 e–
• Second IE = energy to remove from 1+ ion, etc.
M+1(g) + IE2 → M2+(g) + 1 e–


Ionization Energy (IE):
• The larger the effective nuclear charge on the
electron to be removed, the more energy it takes to
remove it.
• The farther the electron most probably is from the
nucleus, the less energy it takes to remove it.
• Trend:
– First IE decreases down the group.
• Valence electron is farther from nucleus.
– First IE generally increases across the period.
• Effective nuclear charge increases.


Summary on First Ionization Energy for
Main-Group Elements
First ionization energy generally
• decreases as we move down a column (or family)
in the periodic table because electrons in the
outermost principal level are increasingly farther
away from the positively charged nucleus and are
therefore held less tightly.
• increases as we move across (left to right) a row
(or period) in the periodic table because electrons in
the outermost principal energy level experience a
greater effective nuclear charge (Zeff).

Summary on First Ionization Energy for
Main-Group Elements
• The strength of attraction is related to the most
probable distance the valence electrons are from
the nucleus and the effective nuclear charge the
valence electrons experience.
• The larger the orbital an electron is in, the farther its
most probable distance will be from the nucleus and
the less attraction it will have for the nucleus.
• Quantum mechanics predicts that the atom’s first
ionization energy should get
– smaller down a column.
• Traversing across a period increases the effective nuclear
charge on the valence electrons.
– larger across a period.
Problem Solving: Ionization Energy
Example 3.9 First Ionization Energy
On the basis of periodic trends, determine which element in each pair has the higher first ionization energy (if possible).
a. Al or S b. As or Sb c. N or Si d. O or Cl
Solution
a. Al or S
S has a higher first ionization energy than Al
because, as you trace the path between Al and
S on the periodic table, you move to the right
within the same row. First ionization energy
increases as you go to the right due to increasing
effective nuclear charge.
b. As or Sb
As has a higher first ionization energy than Sb
because, as you trace the path between As
and Sb on the periodic table, you move down a
column. First ionization energy decreases as
you go down a column as a result of the
increasing size of orbitals with increasing n.

Continued
c. N or Si
N has a higher first ionization energy than Si
because, as you trace the path between N and Si on
the periodic table, you move down a column (first
ionization energy decreases due to increasing size
of outermost orbitals) and then to the left across a
row (first ionization energy decreases due to
decreasing effective nuclear charge). These effects
sum together for an overall decrease.
d. O or Cl
Based on periodic trends alone, it is impossible to
tell which has a higher first ionization energy
because, as you trace the path between O and Cl,
you go to the right across a row (first ionization
energy increases) and then down a column (first
ionization energy decreases). These effects tend to
counter each other, and it is not obvious which will
dominate.

Continued
For Practice 3.9

On the basis of periodic trends, determine the element in each pair with the higher first ionization energy
(if possible).
a. Sn or I b. Ca or Sr c. C or P d. F or S

Arrange the following elements in order of decreasing first ionization energy: S, Ca, F, Rb, Si.

First Ionization Energy: Exceptions to the Trend
• GENERAL trend for first ionization energy of main-group
elements is that as you go across a period, ionization energy
increases.
– Exceptions: 2A to 3A and 5A to 6A
• Exceptions are usually a result of
– the type of orbital (s, p, d, or f) and its shielding ability.
– repulsion factors associated with electrons occupying degenerate
orbitals (i.e., p orbitals).
B has smaller first ionization energy than

Be due to electron position: 2p for B and 2s
for Be.
The electron in 2p orbitals has less shielding

(i.e., less effective nuclear charge factor) and
therefore requires less energy for its removal
than an electron in a 2s orbital.
First Ionization Energy: Exceptions to the Trend
• First ionization energy’s GENERAL trend is that as you go

across a period, ionization energy increases.
To ionize N, you must break up a half-full sublevel, which costs

extra energy.
When you ionize O, you get a half-full sublevel, which costs

less energy.

Trends in Second and Successive Ionization
Energies
• They depend on the number of
valence electrons an element has.
• Removal of each successive
electron costs more energy.
– Shrinkage in size due to having
more protons than electrons
– Outer electrons closer to the
nucleus; therefore harder to
remove
• Regular increase in energy for
each successive valence
electron
• Large increase in energy when
core electrons are removed
Trends in Second and Successive Ionization
Energies

Periodic Trend: Electron Affinities (EA) for
Main-Group Elements
Electron Affinity:
• It is the energy associated with the addition of an
electron to the valence shell of an atom that is in the
gas phase.
M(g) + 1 e− → M1−(g) + EA
• It is defined as exothermic (−) release of energy, but
may actually be endothermic (+) intake of energy.
– Some alkali earth metals’ and all noble gases’ electron
affinities are endothermic.
• The more energy that is released, the larger the
electron affinity.
– The more negative the number, the larger the EA.
Periodic Trend: Electron Affinities (EA)
General Trend for Main-Group Elements:
• EA increases across a period.
– EA becomes more negative from left to right.
• Halogens have the highest EA for any period.

Periodic Trend: Electron Affinities (EA)
Summarizing Electron Affinity for Main-Group Elements
• Most groups (columns) of the periodic table do not exhibit any
definite trend in electron affinity.
• Among the group 1A metals, however, electron affinity becomes
more positive as we move down the column (adding an electron
becomes less exothermic).
– Alkali metals (group 1A) decrease electron affinity down the column.
• Generally irregular increase in EA from second period to third
period
– Group 5A generally has lower EA than expected because extra
electron must pair.
– Groups 2A and 8A generally have very low EA because added
electron goes into higher sublevel or energy level.
• Electron affinity generally becomes more negative (adding an
electron becomes more exothermic) as we move to the right
across a period (row) in the periodic table.
Characteristics of Metals versus Nonmetals
• Metals • Nonmetals
– Malleable and ductile – Brittle in solid state
– Shiny, lustrous, reflect – Dull, nonreflective,
light solid surface
– Conduct heat and – Electrical and thermal
electricity insulators
– Most oxides basic and – Most oxides acidic and
ionic molecular
– Form cations in – Form anions and
solution polyatomic anions
– Lose electrons in – Gain electrons in
reactions—oxidized reactions—reduced

Periodic Trend: Metallic Character
• Metallic character is how closely an element’s
properties match the ideal properties of a metal.
– More malleable and ductile, better conductor, and
easier to ionize
• Metallic character decreases left to right
across a period.
– Metals found at the left of the period and nonmetals to
the right
• Metallic character increases down the column.
– Nonmetals found at the top of the middle main-group
elements and metals found at the bottom


Metallic Elements:
• Ionization energy decreases down the column.
– Very low ionization energies
• Good reducing agents; easy to oxidize
• Very reactive; not found uncombined in nature
• React with nonmetals to form salts
• Compounds generally soluble in water; therefore, metal ions
are found in seawater.
• Electron affinity decreases down the column.
Except for the noble gases, metals generally have
smaller first ionization energies and nonmetals
generally have larger electron affinities.

Metallic Elements:
• Quantum mechanics predicts that the atom’s
metallic character should
– increase down a column because the valence electrons
are not held as strongly.
– decrease across a period because the valence electrons
are held more strongly and the electron affinity increases.
• Atomic radius increases down the column.
• Melting point decreases down the column (groups
1A and 2A).
– All very low MP for metals
• Density increases down the column.
– Except K, Mg, Ca
Ionization Energy Problem
Example 3.10 Metallic Character
On the basis of periodic trends, choose the more metallic element from each pair (if possible).
a. Sn or Te b. P or Sb c. Ge or In d. S or Br
Solution
a. Sn or Te
Sn is more metallic than Te because, as you trace the path
between Sn and Te on the periodic table, you move to the
right within the same period. Metallic character decreases
as you move to the right.
b. P or Sb
Sb is more metallic than P because, as you trace the path
between P and Sb on the periodic table, you move down a
column. Metallic character increases as you move down a
column.

Continued
c. Ge or In
In is more metallic than Ge because, as you trace the path
between Ge and In on the periodic table, you move down a
column (metallic character increases) and then to the left
across a period (metallic character increases). These
effects add together for an overall increase.
d. S or Br
Based on periodic trends alone, we cannot tell which is
more metallic because as you trace the path between S and
Br, you go to the right across a period (metallic character
decreases) and then down a column (metallic character
increases). These effects tend to counter each other, and it
is not obvious which will predominate.

Continued
For Practice 3.10

On the basis of periodic trends, choose the more metallic element from each pair (if possible).
a. Ge or Sn b. Ga or Sn c. P or Bi d. B or N

Arrange the following elements in order of increasing metallic character: Si, Cl, Na, Rb.

A Summary of Elemental Periodic
Properties

Lecture 03

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• During the nineteenth century scientists

• Recurring patterns in physical and chemical

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• Mendeleev (1869) summarized these

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• Rows of the table are referred to as periods.

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• Quantum-mechanical theory describes the

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• However, for multi-electron atoms (all others but the H atom),

• Spin is a fundamental property of all electrons.

• The electron’s spin adds a fourth quantum number to the

• No two electrons in an atom may have the same set

Example: Helium (He)

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• Orbitals that are in the same sublevel have the same

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Write the following electron configurations:

a. Ca a. Ca: 1s22s22p63s23p64s2 or [Ar]4s2

b. Fe b. Fe: 1s22s22p63s23p64s23d6 or [Ar]4s23d6

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Two unpaired electrons

For Practice 3.2

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• One of the most important factors in the way an atom behaves,

Ge 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p2

Ge 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p2

For Practice 3.3

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Se [Ar] 4s2 3d10 4p4

For Practice 3.4

For More Practice 3.4

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For Practice 3.5

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Which atom’s valence electrons experience the greatest

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© 2018 Pearson Education, Inc.