Periodic Relationships Among

the Elements
Chapter 8

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Scientists behind the Periodic Table
• John Newlands (1864) – Law of Octaves
• Dmitri Mendeleev and Lothar Meyer (1869)
- extensive tabulation of the elements
based on the regular, periodic recurrence
of properties

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When the Elements Were Discovered

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Scientists behind the Periodic Table
• Mendeleev’s periodic table included 66
known elements.
• By 1900, some 30 more had been added to
the list, filling in some of the empty spaces.
• Problem arises with inconsistencies in
argon and potassium

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Scientists behind the Periodic Table
• Ernest Rutherford – alpha scattering
experiment
• Henry Moseley (1913) - found that atomic
number increases in the same order as
atomic mass.

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 ns2np6
ns1 Ground State Electron Configurations of the Elements

ns2np1

ns2np2
ns2np3

ns2np4
ns2np5
ns2

d10
d1

d5

4f
5f
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Classification of the Elements

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 Electron Configurations of Cations and Anions
Of Representative Elements

Na [Ne]3s1 Na+ [Ne]

Atoms lose electrons so that
Ca [Ar]4s2 Ca2+ [Ar] cation has a noble-gas outer
electron configuration.
Al [Ne]3s23p1 Al3+ [Ne]

H 1s1 H- 1s2 or [He]

Atoms gain electrons
so that anion has a F 1s22s22p5 F- 1s22s22p6 or [Ne]
noble-gas outer
O 1s22s22p4 O2- 1s22s22p6 or [Ne]
electron configuration.
N 1s22s22p3 N3- 1s22s22p6 or [Ne]
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 Cations and Anions Of Representative Elements
+1
+2

+3

-2
-3

-1
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Isoelectronic: have the same number of electrons, and
hence the same ground-state electron configuration

Na+: [Ne] Al3+: [Ne] F-: 1s22s22p6 or [Ne]

O2-: 1s22s22p6 or [Ne] N3-: 1s22s22p6 or [Ne]

Na+, Al3+, F-, O2-, and N3- are all isoelectronic with Ne

What neutral atom is isoelectronic with H- ?

H-: 1s2 same electron configuration as He

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Electron Configurations of Cations of Transition Metals

When a cation is formed from an atom of a transition metal,

electrons are always removed first from the ns orbital and
then from the (n – 1)d orbitals.

Fe: [Ar]4s23d6 Mn: [Ar]4s23d5

Fe2+: [Ar]4s03d6 or [Ar]3d6 Mn2+: [Ar]4s03d5 or [Ar]3d5
Fe3+: [Ar]4s03d5 or [Ar]3d5

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Effective nuclear charge (Zeff) is the “positive charge” felt by
an electron.

Zeff = Z -  0 <  < Z ( = shielding constant)

Zeff  Z – number of inner or core electrons

Z Core Zeff Radius (pm)

Na 11 10 1 186

Mg 12 10 2 160

Al 13 10 3 143

Si 14 10 4 132 12
 Effective Nuclear Charge (Zeff)

increasing Zeff
increasing Zeff

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 Atomic Radii

metallic radius covalent radius

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15
Trends in Atomic Radii

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Comparison of Atomic Radii with Ionic Radii

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Cation is always smaller than atom from
which it is formed.
Anion is always larger than atom from
which it is formed.
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The Radii (in pm) of Ions of Familiar Elements

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Chemistry in Action: The 3rd Liquid Element?

117 elements, 2 are liquids at 250C – Br2 and Hg

223
Fr, t1/2 = 21 minutes

Liquid?
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Ionization energy is the minimum energy (kJ/mol) required
to remove an electron from a gaseous atom in its ground
state.

I1 + X (g) X+(g) + e- I1 first ionization energy

I2 + X+(g) X2+(g) + e- I2 second ionization energy

I3 + X2+(g) X3+(g) + e- I3 third ionization energy

I 1 < I2 < I3

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22
Variation of the First Ionization Energy with Atomic Number

Filled n=1 shell

Filled n=2 shell

Filled n=3 shell

Filled n=4 shell
Filled n=5 shell

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 General Trends in First Ionization Energies

Increasing First Ionization Energy

Increasing First Ionization Energy

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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- X-(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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26
Variation of Electron Affinity With Atomic Number (H – Ba)

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Diagonal Relationships on the Periodic Table

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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 1A Elements (ns1, n  2)

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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 2A Elements (ns2, n  2)

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 Group 3A Elements (ns2np1, n  2)

4Al(s) + 3O2(g) 2Al2O3(s)

2Al(s) + 6H+(aq) 2Al3+(aq) + 3H2(g)

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Group 3A Elements (ns2np1, n  2)

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 Group 4A Elements (ns2np2, n  2)

Sn(s) + 2H+(aq) Sn2+(aq) + H2 (g)

Pb(s) + 2H+(aq) Pb2+(aq) + H2 (g)

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Group 4A Elements (ns2np2, n  2)

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 Group 5A Elements (ns2np3, n  2)

N2O5(s) + H2O(l) 2HNO3(aq)

P4O10(s) + 6H2O(l) 4H3PO4(aq)

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Group 5A Elements (ns2np3, n  2)

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 Group 6A Elements (ns2np4, n  2)

SO3(g) + H2O(l) H2SO4(aq)

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Group 6A Elements (ns2np4, n  2)

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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 7A Elements (ns2np5, n  2)

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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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 Compounds of the Noble Gases

A number of xenon compounds XeF4, XeO3,

XeO4, XeOF4 exist.
A few krypton compounds (KrF2, for example)
have been prepared.
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 Comparison of Group 1A and 1B

The metals in these two groups have similar outer

electron configurations, with one electron in the
outermost s orbital.
Chemical properties are quite different due to difference
in the ionization energy.

Lower I1, more reactive

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 Properties of Oxides Across a Period

basic acidic

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Chemistry in Action: Discovery of the Noble Gases

Sir William Ramsay

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