Lecture Presentation

Chapter 8

Periodic Properties
of the Elements

Catherine MacGowan
Armstrong Atlantic State University
© 2013 Pearson Education, Inc.
 Periodic Table: Historic Perspective
• Dmitri Mendeleev (1834-1907) developed
the modern periodic table.
– He argued that element properties are
periodic functions of their atomic
weights.

• Periodic law:
law When the elements are
arranged in order of increasing atomic
mass, certain sets of properties recur
periodically.
– Elements having similar physical and
chemical properties fall within a
column.

• We now know that element properties are

periodic functions of their ATOMIC
NUMBERS.

© 2013 Pearson Education, Inc.

 Mendeleev’s Periodic Table

Mendeleev’s “periodic table” allowed for the prediction of

elements not yet discovered based on their physical and
chemical properties.

© 2013 Pearson Education, Inc.

 Periodic Table: Organization

• The elements are arranged from left to right in increasing

ATOMIC NUMBER (number of protons an element has).

• Rows in the periodic table are referred to as PERIODS.

• Columns within the periodic table are sometimes referred to as

families.

– Families because the elements within the column have similar

physical and chemical properties

• The elements, their names, and symbols are given on the

PERIODIC TABLE.

© 2013 Pearson Education, Inc.

 Electron Configuration

A map of atom’s electrons

© 2013 Pearson Education, Inc.

 Electron Configuration
• According to quantum mechanics:

– Electron location around the atom’s nucleus is

described by the four quantum numbers:
• n (principle energy level)
• l (orbital type: s, p, d, f…)
• ml (orientation of orbital)
• ms (spin of electron in orbital)

– No two electrons can have the same four quantum

numbers: Pauli exclusion principle

© 2013 Pearson Education, Inc.

 Writing Atomic Electron Configurations

Electron configuration for He, atomic number = 2

number of
electrons in the
orbital

1 s2
orbital type (value of
l)
Energy level (value of n)

© 2013 Pearson Education, Inc.

 Arrangement of Electrons in Atoms
Electrons are arranged around an
atom’s nucleus according to the
Aufbau principle.

Electrons enter the lowest energy

level (n) and orbitals (l) available.
• n + l rule
•Electrons will enter lowest
energy subshell (l) that is
empty in that energy
level (n).
• Example: 2s vs. 2p
• For 2s: n = 2 and l = 0
(s )
So, (n + l) = 2 = 0 = 2
• For 2p: n = 2 and l = 1
(p )
So, (n + l) = 2 + 1 = 3

The electron goes into the empty

2sPearson
© 2013 orbital,
Education, not
Inc. the 2p.
 General Energy Ordering of Electrons
in Atomic Orbitals

© 2013 Pearson Education, Inc.

 Li: Electron Configuration

Box orbital diagram of Li

Li has an atomic
number of 3, so to
be neutral it must
have 3 electrons.
3 3p
3s
Its electron
configuration is
1s22s1. E
2 2p
2s
1
1s
© 2013 Pearson Education, Inc.
 N: Electron Configuration

N has an atomic number

Box orbital diagram of N
of 7, so to be neutral it
must have 7 electrons.
Its electron configuration
is 1s22s22p3.
3 3p
Here we see for the first 3s
time HUND’S rule.

When placing electrons in E

a set of orbitals having
the same energy
2 2p
(degenerate orbitals), the 2s
electrons are placed
singly as long as 1
possible.
1s
© 2013 Pearson Education, Inc.
 Na: Electron Configuration
Na has an atomic number
of 11, so to be neutral it Box orbital diagram of Na
must have 11 electrons.

Its electron configuration

is 1s22s22p63s1.
3 3p
Another way to write its
electron configuration is 3s
using “noble gas
notation”:
[Ne] 3s1 E
Where the first two 2 2p
energy levels are filled or
the “neon core”
2s
(1s22s22p6) + 3s1
1
1s
© 2013 Pearson Education, Inc.
 Periodic Table and Electron Configuration

© 2013 Pearson Education, Inc.

 Inner Core and Valence Electron
Configuration
• Inner core electrons:
electrons the filled “shells”
• Valence electrons:
electrons electrons occupying the outer
energy level
– These are the electrons that participate in:
• Bonding
• Making cations – lose
• Making anions – gain

Si: 1s22s22p63s23p2
[Ne] 3s23p2

© 2013 Pearson Education, Inc.

 d and f block elements
• Transition metals
– Their valence shell contains d
electrons
• d electrons first appear in the 4th
period
– 3d electrons in 4th period
– 4d electrons in 5th period
– 5d electrons in 6th period
– 6d electrons in 7th period

• Inner transition metals

– Their valence shell contains f
electrons
• f electrons first appear in the 6th
period
– 4f electrons in 6th period
– 5f electrons in 7th period

© 2013 Pearson Education, Inc.

 Anomalous Electron Configurations
• The actual electron configuration of some elements, specifically those
found within the transition and inner transition metal section, have an
arrangement that is not predicted.

• Reason: sublevel splitting

– The (n)s (where n = 4, 5, 6,…) has a lower energy than the (n-1)d
(where n = 3, 4, 5,…) when empty, and therefore electrons enter the
(n)s orbital before the (n-1)d.
• Example: 4s is filled first, then electrons enter the 3d orbital.
– The energy difference between s and d orbitals is not large.
– Also, as the (n-1)d orbitals are filled, their energy level becomes lower
than the (n)s orbitals.

• Anomalous electron configurations occur when:

– the (n)s orbital only partially fills before electrons start entering the
(n−1)d or
– doesn’t fill at all and all electrons are in the (n-1)d orbital

© 2013 Pearson Education, Inc.

16
 Examples of Anomalous
Electron Configurations

Predicted as per Actual as found

Aufbau principle experimentally

Cr = [Ar]4s 3d 2 4 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

© 2013 Pearson Education, Inc.

17
 Electron configurations:
Ions

© 2013 Pearson Education, Inc.

 The “Full-Shell” Look:
Eight Valence Electrons
• Quantum-mechanical calculations show that an atom with eight valence
electrons should be unreactive – meaning the atom is very stable.

• The noble gases have eight valence electrons and are all very stable and
unreactive.
• Exception is Helium (He), which has two valence electrons, but
that fills its valence shell.

• If a “full-shell” look implies stability, then elements having either one

more electron (alkali metals) or one less electron (halogens) should be
predicted to be very reactive.
– Halogens,
Halogens with seven valence electrons, are the most reactive of the
nonmetals.
• They gain ONE electron to form anions.
– Alkali metals,
metals with one more electron than the preceding noble gas,
are the most reactive of the metals.
• They lose ONE electron to form cations.

© 2013 Pearson Education, Inc.

19
 Electron Configuration for Ions
• Electrons are removed or added to the VALENCE SHELL.
– Valence shell is the outermost energy level that an atom’s
electrons occupy.
– Electrons in the valence shell are referred to as the valance
electrons.

• Cations
– Metals tend to form cations.
– Cations are elements having fewer electrons than protons.
– Cations are positively charged atoms.

• Anions
– Nonmetals tend to form anions.
– Anions are elements that have more electrons than protons.
– Anions are negatively charged atoms.

© 2013 Pearson Education, Inc.

 Electron Configuration for Cations

• s column metals (1A, alkali and 2A, alkaline earths) lose their s-valence
electrons.

• Mg [Ne] 3s2 Mg2+ [Ne]

• p block elements (3A-7A or 13-17) lose their p-valence electrons FIRST

and then their s-valence electrons.

• Sn [Kr] 4d10 5s25p2 Sn2+ [Kr] 4d105s2

• Sn [Kr] 4d105s25p2 Sn4+ [Kr] 4d10

• Full d subshells are very stable.

– They behave as pseudo inner (full-shell) core electrons.

© 2013 Pearson Education, Inc.

 Electron Configuration for Cations

• d block elements (1B-2B or 3-12) lose their s-valence electrons FIRST and then their d-
valence electrons.

• Fe [Ar] 3d64s2 Fe2+ [Ar] 3d6

• Fe [Ar] 3d64s2 Fe3+ [Ar] 3d5

*Half-filled d subshells are very stable

• f group elements (lanthanides 58-71 and actinides 90-103) lose their s-valence electrons
FIRST and then their f-valence electrons.

• Bk [Rn] 5f97s2 Bk2+ [Rn] 5f9

• Bk [Rn] 5f97s2 Bk4+ [Rn] 5f7

*Half-filled f subshells are very stable.

© 2013 Pearson Education, Inc.

 Ion Configurations: Anions

• Anions gain electrons.

• Electrons go in the available valance orbitals.

O: [He] 2s22p4
O2-: [He] 2s22p6 or [Ne]

I: [Kr] 4d105s25p5
I- : [Kr] 4d105s25p6 or [Xe]

© 2013 Pearson Education, Inc.

 Magnetic Properties of
Transition Metal Atoms and Ions

• Electron configurations that result in unpaired

electrons mean that the atom or ion will have a net
magnetic field. This is called paramagnetism.
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.
diamagnetism
– Slightly repelled by a magnetic field

© 2013 Pearson Education, Inc.

24
 Why Iron (III) Oxide Is Magnetic

• Ions WITH UNPAIRED ELECTRONS are

PARAMAGNETIC.
• Ions having NO UNPAIRED ELECTRONS are
DIAMAGNETIC.
– Fe3+ ([Ar] 3d5 )in Fe2O3 has five unpaired electrons.

4s 4s
3d 3d
Fe Fe3+

© 2013 Pearson Education, Inc.

 Periodic Trends

© 2013 Pearson Education, Inc.

 Electron Configuration, Element Properties,
and the Periodic Table

• The number of valence electrons largely

determines the behavior of an element.
– Chemical and some physical

• The number of valence electrons follows

a periodic pattern; the properties of the
elements should also be periodic.

© 2013 Pearson Education, Inc.

27
 Effective Nuclear Charge
Effective nuclear charge (Zeff):

• It is the pull/force an electron “feels” from the nucleus (protons).

• The closer the electrons are to the nucleus, the greater the “pull” on
the electrons.

• The greater the Zeff, the more tightly the electrons are held and the
more energy needed to remove the electrons.
– Electrons located farthest from the nucleus (e.g., valence shell)
experience less Zeff.

• Zeff explains the reason for the periodic properties and trends of the
elements.

• Zeff general trend:

Zeff increases going across periods.
Zeff decreases going down periods.

© 2013 Pearson Education, Inc.

 Effective Nuclear Charge, Zeff,
and Screening/Shielding Aspect

• Zeff increases across a period owing

to incomplete shielding by inner
electrons in atomic orbitals
(subshells).

• Shielding ability of subshells:

s>p>d>f

• Estimate Zeff
= [Z (atomic #) - (# inner electrons)]
– Pull felt by 2s electron in Li:
Zeff = 3 - 2 = 1

© 2013 Pearson Education, Inc.

 Zeff Experienced by Outermost Valence
Electron
Observed Predicted
Li +1.28 +1.00 3-2=1
B +2.58 +1.00 5-4=1
C +3.22 +1.00 6-5=1
N +3.85 +1.00 7-6=1
O +4.49 +1.00 8-7=1
F +5.13 +1.00 9-8=1

• Zeff increases as you go across a period due to the ineffective

shielding of the atomic orbitals (subshells) within the period.

• The values observed are different than predicted values.

• Reason: shielding abilities of the atomic orbitals (subshells)

© 2013 Pearson Education, Inc.

 Atomic Radii

© 2013 Pearson Education, Inc.

 Atomic Radii
• Radii (size) increase going
down a group due to
decrease in Zeff.
– As electrons are added in
different levels (shell)
farther from the nucleus,
there is less attraction by
the protons in the nucleus
to the orbiting electrons.

• Radii (size) decrease going

across a period due to the
increase in Zeff.
– Ineffective shielding of
the orbitals (subshells),
resulting in an increase in
attraction by protons in
the nucleus to the orbiting
electrons
© 2013 Pearson Education, Inc.
© 2013 Pearson Education, Inc.
 Which has the larger atomic radius?

a. N or F
b. C or Ge
c. B or Al
d. Li or K

© 2013 Pearson Education, Inc.

 Which has the larger atomic radius?

ANSWER
a. N or F N is because it is more left in the
period.

b. C or Ge Ge is because it is farther down

the column.

c. B or Al Al is because it farther down

the column and to the left in the
period.

d. Li or K K is because it is farther down

the column.
© 2013 Pearson Education, Inc.
 Atomic Radii vs. Cation Radii:
Size Comparison

+
Li, 152 pm Li+, 78 pm
(3 e- and 3 p+) (2 e- and 3 p+)

• CATIONS are SMALLER than the atoms from

which they come.

• The electron/proton attraction has

INCREASED, so size DECREASES.

© 2013 Pearson Education, Inc.

 Ionic Radii: Cations

© 2013 Pearson Education, Inc.

 Atomic Radii vs. Anion Radii:
Size Comparison

-
F, 71 pm F-, 133 pm
(9 e- and 9 p+) (10 e- and 9 p+)

• ANIONS are LARGER than the atoms from which

they come.

• The electron/proton attraction has DECREASED,

so size INCREASES.

© 2013 Pearson Education, Inc.

 Ionic Radii: Anions

© 2013 Pearson Education, Inc.

 Choose the larger of each pair.

• S or S2−

• Ca or Ca2+

• Br− or Kr

© 2013 Pearson Education, Inc.

40
 Answer: Choose the larger of each pair.
• S or S2−
S2− is larger because there are more electrons (18 e−)
for the 16 protons to hold.
The anion is larger than the neutral atom.

• Ca or Ca2+
Ca is larger because its valence shell electrons have
been lost to form Ca2+.
The cation is always smaller than the neutral atom.

• Br− or Kr
Br− is larger because it has fewer protons (35 p+) to
hold the 36 electrons than does Kr (36 p+).
*For isoelectronic species, the more negative the
charge, the larger the atom or ion.

* An isoelectronic series is elements or ions having the

same electronic configuration.

© 2013 Pearson Education, Inc.

41
 General Periodic Trend for
1st Ionization Energy
IE is the energy required to remove an
electron from an atom in the gas phase.

• 1st IE increases across a period

because Zeff increases due to poor
shielding ability of p electrons.

• 1st IE decreases going down a

column due to increase in atomic
size and decrease in Zeff.
– This is why metals lose
electrons more easily than
nonmetals and are good
reducing agents.
• Have lower 1st IE
– Nonmetals lose electrons with
difficulty.
• Have higher 1st IE

© 2013 Pearson Education, Inc.

 Periodic Trend: Ionization Energy (IE)

IE is endothermic, H (+), in nature.

1st IE: Mg(g) + 738 kJ  Mg+(g) + e-

2nd IE: Mg+(g) + 1451 kJ  Mg2+(g) + e-

3rd IE: Mg2+(g) + 7733 kJ  Mg3+(g) + e-

NOTE:
– Mg+ has 12 protons and only 11 electrons.

• Therefore, 1st IE for Mg+ > Mg.

– Mg2+ has 12 protons and only 10 electrons.
• Therefore, 2nd IE for Mg2+ > Mg+.
– Energy cost is VERY high to dip into a full
(inner core) shell (lower zx).

© 2013 Pearson Education, Inc.

 Trends in 1st Ionization Energy

© 2013 Pearson Education, Inc.

 Choose the atom in each set having the
higher 1st ionization energy.

a. Al or S
b. As or Sb
c. N or Si

© 2013 Pearson Education, Inc.

45
 Answers: Choose the atom in each set
having the higher 1st ionization energy.

ANSWER
a. Al or S sulfur
b. As or Sb arsenic
c. N or Si nitrogen

© 2013 Pearson Education, Inc.

46
 General Trends in Electron Affinity (EA)

Electron affinity is the change in energy (E) involved when a

atom gains an electron to form an anion.

A(g) + e-  A-(g) EA is about a ∆E

• EA can be either endothermic or exothermic in nature.

– Why either energy exchange?
• It is due to electron-electron repulsion within orbitals
and the volume of the atom.

• General trends:
– EA increases across a period.
• EA becomes more positive due to increase in Zeff.

– EA decreases down a group.

• EA becomes less positive due to decrease in Zeff.

© 2013 Pearson Education, Inc.

 General Trends in Electron Affinity (EA)

Electron affinity is the willingness to

accept electrons into the valence shell.

• The fluoride ion has a LOWER EA

than the chloride ion because it has
a smaller volume and greater e e
than chloride.

• EA greatest for halogens

• EA greater for nonmetals vs. metals

• A LARGER EA value means a very

STABLE ion.
– Larger EA is more negative energy
• More stable

© 2013 Pearson Education, Inc.

 1st and 2nd Electron Affinity of Oxygen

O atom: ∆E is for the first EA is

[He]     EXOthermic because
oxygen has an affinity for
an electron (-141 kJ/mole).
+ electron
1st EA = -141 kJ
O- ion:
[He]    

E for second EA is
ENDOthermic because of
O2- ion: increase in electron-
    electron repulsion (780
[He] kJ/mol).
2nd EA = +780 kJ

© 2013 Pearson Education, Inc.

 Properties of Metals and Nonmetals

Metal element Nonmetal element

characteristics characteristics

• Malleable and ductile • Brittle in solid state

• Shiny, lustrous, reflect • Dull, nonreflective solid
light surface
• Conduct heat and • Electrical and thermal
electricity insulators
• Most oxides are basic and • Most oxides are acidic
ionic and molecular.
• Form cations in solution • Form anions and
• Lose electrons in polyatomic anions
reactions • Gain electrons in
– oxidized reactions
– reduced

© 2013 Pearson Education, Inc.

© 2013 Pearson Education, Inc.
 Metallic Character

• Metallic character of an element is about how closely its

properties match the ideal properties of a metal.
– The more malleable and ductile, the better the
conductor and easier to ionize.

• Metallic character decreases from left to right across a

period.
– Metals are found at the left of the period and nonmetals
are to the right.

• Metallic character increases down the column.

– Nonmetals are found at the top of the middle main-
group elements and metals are found at the bottom.

© 2013 Pearson Education, Inc.

52
 Metallic Trend

© 2013 Pearson Education, Inc.