CH4701/4001

2019

Lecture 16 and 17

Trends in the Periodic Table

Dr Sarah Hudson
MS2-019
Department of Chemical Sciences
Bernal Institute
University of Limerick
The Periodic Table of the Elements
 The Periodic Table

The properties of an element depend upon the electronic configuration of the atom

The Periodic Table (P.T.)

A system where elements of similar e- configuration (and hence chemistry) are grouped
together

Structure of P.T.

• arrange rows (periods) in order of filling of electronic orbitals (1 row per principle
quantum level or "shell")

• arrange columns (groups) so that elements with the same outer e- configuration are
above one another
Periodic Table of Mendeleev and Mayer (1872)

1s
2s 2p
3s 3p
4s 3d 4p
5s 4d 5p
6s 4f 5d 6p
7s 5f 6d 7p

s f d p

'blocks'
f orbitals only in n = 4 shells and higher
l=3
ml = -3, -2, -1, 0, 1, 2,3
 Structure of P.T.
● arrange rows (periods) in order of filling of electronic orbitals (1 row
per principle quantum level or "shell")
● arrange columns (groups) so that elements with the same outer e-
configuration are above one another
Structure of P.T.
● arrange rows (periods) in order of filling of electronic

orbitals (1 row per principle quantum level or "shell")

● arrange columns (groups) so that elements with the

same outer e- configuration are above one another

Atomic radii:
electron clouds are diffuse

atoms - defined radius

Atomic radii:

electron clouds are diffuse

atoms - defined radius

2r 2r

Cl2 r = 99 pm C-C r = 77 pm

C-Cl d predicted to be 176 pm, experimentally d = 178 pm

Periodic Trends in Atomic Radii
• As a consequence of the ordering in the periodic table,
properties of elements vary periodically.
Periodic Trends in Atomic Radii
• As a consequence of the ordering in the periodic table,
properties of elements vary periodically.

• Atomic size varies consistently through the periodic table.

• Moving down a group, the atoms become larger.

• Moving across a period, atoms become smaller.

Periodic Trends in Atomic Radii
• As a consequence of the ordering in the periodic table,
properties of elements vary periodically.

• Atomic size varies consistently through the periodic table.

• Moving down a group, the atoms become larger.

• Moving across a period, atoms become smaller.

• There are two factors at work:

• principal quantum number, n, and
• the effective nuclear charge, Zeff.
 Trends in the Periodic Table

• As the principle quantum number increases (i.e., move down a group), the distance of the
outermost electron from the nucleus becomes larger. Hence, the atomic radius increases.
 Trends in the Periodic Table

• As the principle quantum number increases (i.e., move down a group), the distance of the
outermost electron from the nucleus becomes larger. Hence, the atomic radius increases.

• Moving across the periodic table, the number of core electrons remains constant. However,
the nuclear charge increases. Therefore, there is an increased attraction between the nucleus
and the outermost electrons. This attraction causes the atomic radius to decrease.
 Trends in the Periodic Table
Atomic radius:

● decreases across periods,

increasing nuclear charge

● increases down groups

increased principal quantum number, n

increased screening of outer e- 's
 Trends in the Periodic Table
Atomic radius:
 Trends in the Sizes of Ions

• Ion size is the distance between ions in an ionic compound.

• Ion size also depends on nuclear charge, number of

electrons, and orbitals that contain the valence electrons.
 Trends in the Sizes of Ions

• Ion size is the distance between ions in an ionic compound.

• Ion size also depends on nuclear charge, number of

electrons, and orbitals that contain the valence electrons.

• Cations vacate the most spatially extended orbital and are

smaller than the parent ion.

• Anions add electrons to the most spatially extended orbital

and are larger than the parent ion.
 Ionization Energy
• The first ionization energy, I1, is the amount of energy required to remove an electron
from a gaseous atom:
Na(g) ® Na+(g) + e-.
 Ionization Energy
• The first ionization energy, I1, is the amount of energy required to remove an
electron from a gaseous atom:

Na(g) ® Na+(g) + e-.

• The second ionization energy, I2, is the energy required to remove an

electron from a gaseous ion:

Na+(g) ® Na2+(g) + e-.

• The larger ionization energy, the more difficult it is to remove the electron.
 Variations in Successive Ionization Energies

• There is a sharp increase in ionization energy when a core

electron is removed.
 Periodic Trends in Ionization Energies

• Ionization energy decreases down a group.

• This means that the outermost electron is more readily

removed as we go down a group.
Periodic Trends in Ionization Energies

• Ionization energy decreases down a group.

• This means that the outermost electron is more readily

removed as we go down a group.

• As the atom gets bigger, it becomes easier to remove an

electron from the most spatially extended orbital.
• Ionization energy generally increases across a period.
• Moving across a period, Zeff increases. Therefore, it
becomes more difficult to remove an electron.
Periodic Trends in Ionization Energies

• Ionization energy decreases down a group.

• This means that the outermost electron is more readily

removed as we go down a group.

• As the atom gets bigger, it becomes easier to remove an

electron from the most spatially extended orbital.
• Ionization energy generally increases across a period.
• Moving across a period, Zeff increases. Therefore, it
becomes more difficult to remove an electron.
Decreases
• Two exceptions: removing the first p electron and removing
the fourth p electron.
Periodic Table of the Elements
Trends in Ionization Energies (Potentials) for Neutral Atoms
.

This more detailed plot of the ioniza

 Electron Configuration of Ions

• Cations: electrons removed from orbital with highest

principle quantum number, n, first:
Li (1s2 2s1) Þ Li+ (1s2)
Fe ([Ar]3d6 4s2) Þ Fe3+ ([Ar]3d5)
Electron Configuration of Ions

• Cations: electrons removed from orbital with highest

principle quantum number, n, first:
Li (1s2 2s1) Þ Li+ (1s2)
Fe ([Ar]3d6 4s2) Þ Fe3+ ([Ar]3d5)

• Anions: electrons added to the orbital with highest n:

F (1s2 2s2 2p5) Þ F- (1s2 2s2 2p6)
 Electron Affinity

• Electron affinity is the opposite of ionization energy.

• Electron affinity is the energy change when a gaseous atom gains an electron to form a
gaseous ion:
Cl(g) + e- ® Cl-(g)
Electron Affinities
• Formation of a negative ion occurs when an electron from some external source
enters the atom and become incorporated into the lowest energy orbital that
possesses a vacancy.
• Because the entering electron is attracted to the positive nucleus, the formation
of negative ions is usually exothermic.

• The energy given off is the electron affinity of the atom.

• For some atoms, the electron affinity appears to be slightly negative, suggesting
that electron-electron repulsion is the dominant factor in these instances
 Electronegativity
Measure of the attraction of an atom for electrons in a bond
increases across periods, decreases down groups

increasing nuclear charge increasing atomic size

& less efficient screening
 Polar covalent bonds
Since oxygen
When there is is more difference
a large electronegative
betweenthanthe
hydrogen,
the molecular orbital
electronegativities of formed
the two will be asymmetrical,
elements with
involved in the
the bonding
bond, electrons
the bonding more likely
molecular to will
orbital be found
be around
the δ– oxygen atom.
asymmetrical.

Example: water δ–

O δ+
δ+

H H
Metals, Nonmetals, and Metalloids
Metals
• Metallic character refers to the properties of metals (shiny or
lustrous, malleable and ductile, oxides form basic ionic
solids, and tend to form cations in aqueous solution).
Metals
• Metallic character refers to the properties of metals (shiny or
lustrous, malleable and ductile, oxides form basic ionic
solids, and tend to form cations in aqueous solution).

• Metallic character increases down a group.

• Metallic character decreases across a period.

Metals
• Metallic character refers to the properties of metals (shiny or
lustrous, malleable and ductile, oxides form basic ionic
solids, and tend to form cations in aqueous solution).

• Metallic character increases down a group.

• Metallic character decreases across a period.

• Metals have low ionization energies.

• Most neutral metals are oxidized rather than reduced.

Metals
• When metals are oxidized they tend to form characteristics
cations.

• All group 1A metals form M+ ions.

• All group 2A metals form M2+ ions.

Metals
• When metals are oxidized they tend to form characteristics
cations.

• All group 1A metals form M+ ions.

• All group 2A metals form M2+ ions.

• Most transition metals have variable charges.

• Most metal oxides are basic:

Metal oxide + water ® metal hydroxide

Na2O(s) + H2O(l) ® 2NaOH(aq)
Nonmetals
• Nonmetals are more diverse in their behavior than metals.
Nonmetals
• Nonmetals are more diverse in their behavior than metals.

• When nonmetals react with metals, nonmetals tend to gain

electrons:

metal + nonmetal ® salt

2Al(s) + 3Br2(l) ® 2AlBr3(s)
Nonmetals
• Nonmetals are more diverse in their behavior than metals.

• When nonmetals react with metals, nonmetals tend to gain

electrons:

metal + nonmetal ® salt

2Al(s) + 3Br2(l) ® 2AlBr3(s)

• Most nonmetal oxides are acidic:

nonmetal oxide + water ® acid
P4O10(s) + H2O(l) ® 4H3PO4(aq)
Metalloids

• Metalloids have properties that are intermediate between

metals and nonmetals.
Metalloids

• Metalloids have properties that are intermediate between

metals and nonmetals.

• Example: Si has a metallic luster but it is brittle.

Metalloids

• Metalloids have properties that are intermediate between

metals and nonmetals.

• Example: Si has a metallic luster but it is brittle.

• Metalloids are extensively used in the semiconductor

industry.
 Characteristics of metals and nonmetals
Metals
Physical properties
good conductors of electricity
ductile
malleable, lustrous
typically: solid
high melting point
good conductors of heat
Chemical properties
react with acids
form basic oxides
(react with acids)
form cations
form ionic halides
Nonmetals
poor conductors of electricity
not ductile
not malleable
solid, liquid or gas
low melting point
poor conductors of heat
do not react with acids
form acidic oxides
(react with bases)
form anions
form covalent halides
 Properties of the Elements

s block
• metallic

• reactive-elements have low ionisation energies (e can

-

be lost readily) - e.g. Na reacts violently with water

p block
• metals, metalloids and non-metals

• not as reactive as s block, e.g. Sn used in alloys

• moving across a period, elements have greater tendency

to form molecular compounds with each other and to react

with metals to form anions, e.g., Cl2 and NaCl

d block
• transition elements

• metals

• can have variety of oxidation states, e.g. Cu , Cu

+ 2+