Chapter 8

Periodic
Relationships
Among the Elements

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When the Elements Were Discovered

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Ground State Electron Configurations of
the Elements

ns2(n-1)d10
ns1(n-1)d10
ns1(n-1)d5
ns2(n-1)d5

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Classification of the Elements

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 …………

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 Example 8.1 (1 of 3)
An atom of a certain element has 15 electrons. Without
consulting a periodic table, answer the following
questions:

a) What is the ground-state electron configuration of the

element?

b) How should the element be classified?

c) Is the element diamagnetic or paramagnetic?

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 Example 8.1 (2 of 3)
Strategy
a) We refer to the building-up principle discussed in
Section 7.9 and start writing the electron configuration with
principal quantum number n = 1.and continuing upward until
all the electrons are accounted for.

b) What are the electron configuration characteristics of

representative elements? transition elements? noble gases?
ns1-2 or ns2np1-5 ns1-2 (n-1d1-10) ns2np6
c) Examine the pairing scheme of the electrons in the outermost
shell. What determines whether an element is diamagnetic or
paramagnetic?
Hund’s rule & Orbital diagram

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 Example 8.1 (3 of 3)
Solution
a) We know that for n = 1 we have a 1s orbital (2 electrons); for n = 2
we have a 2s orbital (2 electrons) and three 2p orbitals (6
electrons); for n = 3 we have a 3s orbital (2 electrons). The number
of electrons left is 15 – 12 = 3 and these three electrons are placed
in the 3p orbitals. The electron configuration is
1s 2 2s 2 2 p 6 3s 2 3 p 3
b) Because the 3p subshell is not completely filled, this is a
representative element. Based on the information given, we cannot
say whether it is a metal, a nonmetal, or a metalloid.

c) According to Hund’s rule, the three electrons in the 3p orbitals have

parallel spins (three unpaired electrons). Therefore, the element is
paramagnetic. (See slide no25 chapter-7 again if you forgot)

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Representative Electron Configurations of
Cations and Anions

Atoms lose electrons so

Na Ne3s1 Na  Ne
Ca Ar 4s 2 Ca2  Ar 
that cation has a noble - gas
Al Ne3s 2 3 p1 Al3  Ne outerelectron configuration.

Atoms gain electrons so that H 1s1 H 1s 2 or He

F 1s 2 2s 2 2 p5 F  1s 2 2s 2 2 p 6 or Ne
anion has a noble - gas
O 1s 2 2s 2 2 p 4 02  1s 2 2s 2 2 p 6 or Ne
outer electron configuration.
N 1s 2 2s 2 2 p3 N3 1s 2 2s 2 2 p 6 or Ne

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Cations and Anions Of Representative
Elements

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 Isoelectronic Species

Isoelectronic: have the same number of electrons, and

hence the same ground-state electron configuration

Na  : Ne Al3  : Ne F- : 1s 2 2s 2 2 p 6 or Ne

- 2 2s 2 2p6 or Ne -
o
O
2 : 1s N : 1s 2 2s 2 2 p 6 or Ne
3

 3  - 2 - 3 -
Na , Al , F , o
O , and N are all isoelectronic with Ne
They have the same number
of electrons when ionizes
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 Electron Configurations of Cations of
Transition Metals
When cation is formed from an atom of a transition metal, electron
are always removed first from the ns orbital and then from (n-1)d
orbitals

Electron remove first from nS orbital

Fe : [Ar]4s 2 3d 6 Mn : [Ar]4s 2 3d 5
Fe2  : [Ar]4s 0 3d 6 or [Ar]3d 6 Mn 2  : [Ar]4s 0 3d 5 or [Ar]3d 5
Fe3  : [Ar]4s 0 3d 5 or [Ar]3d 5

Then remove from (n-1) d

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

Zeff  Z - σ 0  σ  Z (σ  shielding constant)

Zeff  Z – number of inner or core electrons

Z Core Z eff Radiuspm

Na 11 10 1 186

Mg 12 10 2 160

Al 13 10 3 143

Si 14 10 4 132

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Effective Nuclear Charge (Zeff)

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 Atomic Radii (1 of 2)

covalent radius
metallic radius

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Atomic Radii (2 of 2)

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Trends in Atomic Radii

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 Example 8.2 (1 of 2)

Referring to a periodic table, arrange the following

atoms in order of increasing atomic radius: P, Si, N.

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Periodic Table

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 Example 8.2 (2 of 2)
Strategy
What are the trends in atomic radii in a periodic group and in a particular period?
Which of the preceding elements are in the same group? in the same period?

Solution
From Figure 8.1 we see that N and P are in the same group (Group 5A).
Therefore, the radius of N is smaller than that of P (atomic radius increases as we
go down a group).

Both Si and P are in the third period, and Si is to the left of P. Therefore, the
radius of P is smaller than that of Si (atomic radius decreases as we move from
left to right across a period).

Thus, the order of increasing radius is

N<P<Si

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Comparison of Atomic Radii with Ionic
Radii

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 Ion Size

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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 The Radii (in pm) of Ions of Familiar
Elements Long Description
Metals lose electrons, and the cations formed are smaller than
the parent atoms. As the ion charge increases, the size of the
cation decreases for a given atom. For example, the iron(III) ion
is smaller than the iron(II) ion. Also, the size of the cation
generally decreases across a row. For example, the cesium ion
with a charge of +1 is larger than the barium ion with a charge of
+2.
Nonmetals tend to gain electrons, and the anions formed are
larger than the parent atoms. As the ion charge increases, the
size of the anion increases within a row. For example, the nitride
ion has a 3- charge and is larger than the oxide ion with a 2-
charge.

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 Example 8.3 (1 of 3)

For each of the following pairs, indicate which one of the

two species is larger:

(a ) N3  or F2
F-

(b ) Mg2  or Ca2 

(c ) Fe2  or Fe3 

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Periodic Table

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 Example 8.3 (2 of 3)
Strategy
In comparing ionic radii, it is useful to classify the ions into three
categories:

1) isoelectronic ions

2) ions that carry the same charges and are generated from atoms of the
same periodic group, and

3) ions that carry different charges but are generated from the same
atom.

In case (1), ions carrying a greater negative charge are always larger; in
case (2), ions from atoms having a greater atomic number are always
larger; in case (3), ions having a smaller positive charge are always larger.
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 Example 8.3 (3 of 3)
Solution
a) N3- and F- are isoelectronic anions, both containing 10 electrons.
Because N3- has only seven protons and F−has nine, the smaller
attraction exerted by the nucleus on the electrons results in a larger
N3- ion.

b) Both Mg and Ca belong to Group 2A (the alkaline earth metals).

Thus, Ca2+ ion is larger than Mg2+ because Ca’s valence electrons
are in a larger shell (n = 4) than are Mg’s (n = 3).

c) Both ions have the same nuclear charge, but Fe2+ has one more
electron (24 electrons compared to 23 electrons for Fe 3+ ) and hence
greater electron-electron repulsion. The radius of Fe 2+ is larger.

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 Ionization Energy
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

I 2  X ( g )  X2 ( g )  e  I 2 second ionization energy

I 3  X 2  ( g )  X3  ( g )  e  I3 third ionization energy

I1  I 2  I3

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 Ionization Energies

Table 8.2 The Ionization Energies (kJ/mol) of the First 20 Elements

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 Ionization Energies Long Description

The second ionization energy is the energy required to remove a

second electron from the gaseous cation. The third ionization energy is
the energy required to remove a third electron, and so on and so forth.
Generally, ionization energy increases as more electrons are removed
(first IE is lowest, then second IE, then third, etc.).
When evaluating the ionization energies of a given element, the
ionization energies corresponding to valence electrons are much lower
than those associated with core electrons. For example, C has 6
electrons. The first, second, third, and fourth ionization energies are
lower (1086, 2350, 4620, and 6220 kJ/mol, respectively) because they
correspond to the four valence electrons of the C atom. The fifth
(38000 kJ/mol) and sixth (47261 kJ/mol) ionization energies are much
higher and correspond to removal of the two core electrons of the C
atom.
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Variation of the First Ionization Energy
with Atomic Number

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Periodic Table

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General Trends in First Ionization
Energies

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 Example 8.4 (1 of 4)
a) Which atom should have a smaller first ionization energy:
oxygen or sulfur?

b) Which atom should have a higher second ionization

energy: lithium or beryllium?

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 Example 8.4 (2 of 4)
Strategy
a) First ionization energy decreases as we go down a group because
the outermost electron is farther away from the nucleus and feels
less attraction.

b) Removal of the outermost electron requires less energy if it is

shielded by a filled inner shell.

Solution
c) Oxygen and sulfur are members of Group 6A. They have the same
valence electron configuration (ns2 np4), but the 3p electron in
sulfur is farther from the nucleus and experiences less nuclear
attraction than the 2p electron in oxygen. Thus, we predict that
sulfur should have a smaller first ionization energy.
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 Example 8.4 (3 of 4)
b) The electron configurations of Li and Be are 1s22s1and 1s22s2,
respectively. The second ionization energy is the minimum energy
required to remove an electron from a gaseous unipositive ion in
its ground state. For the second ionization process, we write

Li  g   Li2  g   e -
1s 2 1s1
Be   g   Be2  g   e -
1s12s2s
1 1 1
2s 1s 2

Because 1s electrons shield 2s electrons much more effectively than

they shield each other, we predict that it should be easier to remove
a 2s electron from Be+ than to remove a 1s electron from Li+.

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 Example 8.4 (4 of 4)

Check
Compare your result with the data shown in Table 8.2.

In (a), is your prediction consistent with the fact that the

metallic character of the elements increases as we move
down a periodic group?

In (b), does your prediction account for the fact that alkali
metals form +1 ions while alkaline earth metals form +2
ions?

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 Electron Affinity
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  ΔH  - 328 kJ/mol EA   328 kJ/mol

O g   e   O  g  ΔH  - 141 kJ/mol EA   141 kJ/mol

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 Electron Affinities
Table 8.3 Electron Affinities (kJ/mol) of Some Representative Elements and
the Noble Gases*

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

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Periodic Table

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Variation of Electron Affinity With Atomic
Number (H – Ba) Long Description
There are, however, many exceptions to this general rule.
Within a row, halogens have the highest electron affinity,
but the noble gases have the lowest electron affinity. This
makes sense: an electron added to a halogen will result in
the species having a full n level shell, while an electron
added to a noble gas must enter the next n level, as noble
gases already have a full n level shell.

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 Example 8.5 (1 of 2)
Why are the electron affinities of the alkaline earth metals,
shown in Table 8.3, either negative or small positive values?

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 Example 8.5 (2 of 2)
Strategy
What are the electron configurations of alkaline earth metals? Would the added
electron to such an atom be held strongly by the nucleus?

Solution
The valence electron configuration of the alkaline earth metals is ns2, where n is
the highest principal quantum number. For the process

M g  e   M  g
ns 2 ns 2np1

where M denotes a member of the Group 2A family, the extra electron must enter
the np subshell, which is effectively shielded by the two ns electrons (the ns
electrons are more penetrating than the np electrons) and the inner electrons.
Consequently, alkaline earth metals have little tendency to pick up an extra
electron.

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 End of Presentation

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