Lecture 05

Periodicity

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PeriodicTable
Periodic Table

 In 1871, the Russian chemist Dmitri Mendeleev published

the most successful of these organizing schemes in the
form of a table:
 The elements are listed by increasing atomic mass,
 Elements with similar chemical properties in the same
column.

 The modern periodic table of the elements (based on

Mendeleev's earlier version)
 arranged by atomic number, not mass
 one of the great classifying schemes in science
 an indispensable tool to chemists.

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Earliest Periodic Table

http://www.news.cornell.edu/stories/June06/Mendeleev.jpg
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Earliest Periodic Table

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Modern Periodic Table – Element Types

metal nonmetal

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Modern Periodic Table – Element Types

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Modern Periodic Table – Electron Configuration

A periodic table of
ground-state
electron configurations

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Modern periodic table – Rows and Columns

Main group (column):

Group number
= number of valence electrons

Period (row):
Period number
8 = number of energy levels (shells)
Periodicity

Design materials Periodicity

Derived from

Electron Determined by
Aufbau Principle
configuration

Coulomb’s Law

First Ionization
Typical ionic charge

Electro negativity

Atomic and Ionic radii

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General Periodic Trends
 Atomic and ionic size
 Ionization energy
 Electron Affinity
 Metallic behavior
 Electronegativity

Higher effective nuclear charge

Electrons held more tightly

Larger orbitals.
Electrons held less tightly

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Effective Nuclear Charge, Zeff
Effective nuclear charge: “positive charge” felt by an (valence) electron

Zeff = Z – σ,
where 0 < σ < Z (σ = shielding constant)

Zeff ≈ Z – number of inner/core electrons

Zeff of carbon = 6(protons) – 2(electrons) = 4 (positive)

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 Effective Nuclear Charge, Zeff

Zeff 1 4 5 6

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Effective Nuclear Charge, Zeff

Z No. core e- Zeff Radius

Na 11 10 1 186

Mg 12 10 2 160

Al 13 10 3 143

10 core electrons
Si 14 10 4 118

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Effective Nuclear Charge, Zeff

A sodium atom A sodium cation

Na Na+
10 core electrons No. of core electrons?

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Effective Nuclear Charge, Zeff

increasing Zeff
increasing Zeff

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Metallic and Covalent Radius

The metallic radius is The covalent radius is one- In a covalent compound,

one-half the distance half the distance between the bond length and
between nuclei of bonded nuclei in a molecule known covalent radii are
adjacent atoms in a of the element (one-half the used to determine other
crystal of the element bond length) radii.

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Trends in Atomic Size

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18
Row 2

Row 3

Row 4

Row 5
Trends in Atomic Size

Row 6
Trends in Atomic Size

Size goes UP on going down a group.

Because electrons are added further from the nucleus, there
is less attraction. This is due to additional energy levels and
the shielding effect. Each additional energy level “shields”
the electrons from being pulled in toward the nucleus

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Trends in Atomic Size

Size decreases across a period owing to increase in

the effective nuclear charge.

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Ionic Radii

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Ionic Radii

Cation (positively-charged ion)

is always smaller than atom from which it is formed.

Anion (negatively-charged ion)

is always larger than atom from which it is formed.

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Ionic vs. Atomic Radii (01)

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Summary on atomic size

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Ionic vs. Atomic Radii (02)
 Ionic size increases down
a group.

 Ionic size decreases

across a period but
increases from cations to
anions.

 Ionic size decreases as

charge increases for
different cations of a
given element.

 Ionic size decreases with

increasing positive (or
decreasing negative)
charge in an isoelectronic
series.
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Ionization energy

The minimum energy (kJ/mol) required to remove an electron

from a gaseous atom in its ground state.

IE1 + X(g) X+(g) + e- IE1 first ionization energy

IE2 + X+(g) X2+(g) + e- IE2 second ionization energy

IE3 + X2+(g) X3+(g) + e- IE3 third ionization energy

IE1 < IE2 < IE3

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The ionization Energies

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Periodicity of first ionization energy (IE)

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General Trend in First Ionization Energies

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Electron Affinity (EA)
Electron affinity is the negative of the energy change that
occurs when an electron is accepted by an atom in the
gaseous state to form an anion.

X (g) + e- X-(g)

F (g) + e- F-(g) ∆H = -328 kJ/mol EA = +328 kJ/mol

O (g) + e- O-(g) ∆H = -141 kJ/mol EA = +141 kJ/mol

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Electron Affinity

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Electron Affinity

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Electron Affinity

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Metallic behavior

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Metallic behavior

Metals are located in the left and lower three-quarters of the periodic
table. They typically:
 are shiny solids with moderate to high melting points,
 are good thermal and electrical conductors,
 can be drawn into wires and rolled into sheets and
 tend to lose electrons to nonmetals
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Metallic behavior

Nonmetals are located in the upper right quarter of the table. Typically:
 are not shiny,
 have relatively low melting points,
 are poor thermal and electrical conductors,
 are mostly crumbly solids or gases, and
 tend to gain electrons from metals
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Metallic behavior

Metalloids are located in the region between the other two classes and
have properties between them as well
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Trends in metallic behavior

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Electronegativity, χ

χ is a measure of the ability of an atom in a

molecule to attract electrons to itself.

Pauling scale (from bond energies)

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Electronegativity, χ

Electronegativity values for the elements according to Pauling

Trends for electronegativities are the opposite of the trends defining

metallic character: Nonmetals have high values of electronegativity,
the metalloids have the intermediate values, and the metals have low
values.
Electronegativity generally increases up a group and across a period.

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Periodic Trends: Electronegativity

In a group: Atoms with fewer energy levels

can attract electrons better (less shielding).
So, electronegativity increases UP a group of
elements.

In a period: More protons, while the energy

levels are the same, means atoms can better
attract electrons. So, electronegativity
increases RIGHT in a period of elements.

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Group 1A Elements (ns1, n ≥ 2)

M M+1 + 1e-

2M(s) + 2H2O(l) 2MOH(aq) + H2(g)

4M(s) + O2(g) 2M2O(s)

Increasing reactivity

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Group 2A Elements (ns2, n ≥ 2)

M M+2 + 2e-

Be(s) + 2H2O(l) No Reaction

Mg(s) + 2H2O(g) Mg(OH)2(aq) + H2(g)

M(s) + 2H2O(l) M(OH)2(aq) + H2(g) M = Ca, Sr, or Ba

Increasing reactivity

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Group 7A Elements (ns2np5, n ≥ 2)

X + 1e- X-1

X2(g) + H2(g) 2HX(g)

Increasing reactivity
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Group 8A Elements (ns2np6, n ≥ 2)

Completely filled ns and np subshells.

Highest ionization energy of all elements.
No tendency to accept extra electrons.

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Noble gases

Sir William Ramsay

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Properties of Oxides Across a Period

basic acidic

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Summary on major trends

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Modern periodic table – Element type (1)

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End of lecture 05

Thank you!

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