Chemistry

The Molecular Nature of Matter and

Change Eighth Edition

Martin S. Silberberg and Patricia G. Amateis

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 Electron Configuration and Chemical
Periodicity
• 8.1 Characteristics of Many-Electron Atoms
• 8.2 The Quantum-Mechanical Model and the
Periodic Table
• 8.3 Trends in Three Atomic Properties
• 8.4 Atomic Properties and Chemical Reactivity

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 The Effect of Electron Spin

Figure 8.1

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 Summary of Quantum Numbers of Electrons in Atoms

Name Symbol Permitted Values Property

Positive integers Orbital energy
Principal n
(1, 2, 3, . . .) (size)
Orbital shape
(The l values 0, 1,
2,
Angular Integers from 0 to
l and 3 correspond
momentum n−1
to s, p, d, and f
orbitals,
respectively.)
ml Integers from −l to Orbital
Magnetic
0 to +l orientation
ms Direction of e−
Spin + 1 2 or − 1 2
spin

Table 8.1

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 Quantum Numbers and The Exclusion Principle
• Each electron in any atom is described completely by a set of
four quantum numbers.
– The first three quantum numbers describe the orbital, while the fourth
quantum number describes electron spin.
• Pauli’s exclusion principle states that no two electrons in the
same atom can have the same four quantum numbers.
• An atomic orbital can hold a maximum of two electrons and
they must have opposing spins.

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 Factors Affecting Atomic Orbital Energies
• The energies of atomic orbitals are affected by
– nuclear charge (Z) and
– shielding by other electrons.

• A higher nuclear charge increases nucleus-electron

interactions and lowers sublevel energy.
• Shielding by other electrons reduces the full nuclear
charge to an effective nuclear charge (Zeff).
– Zeff is the nuclear charge an electron actually experiences.

• Orbital shape also affects sublevel energy.

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 The Effect of Nuclear Charge on Sublevel Energy
• Greater nuclear
charge lowers
sublevel energy.

• It takes more energy

to remove the 1s
electron from He+
than from H.

Figure 8.3
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 Shielding and Orbital Energy
• Electrons in the same energy level shield each other to
some extent.
• Electrons in inner energy levels shield the outer
electrons very effectively.
– The farther from the nucleus an electron is, the lower the Zeff for
that particular electron.

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 Shielding and Energy Levels

Figure 8.4
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 Penetration and Sublevel Energy
• Orbital shape causes
electrons in some
orbitals to “penetrate”
close to the nucleus.

• Penetration increases
nuclear attraction and
decreases shielding.

Figure 8.4

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 Values of Zeff for the Sublevels in Potassium (Z = 19)

Sublevel Zeff

1s 18.49

2s 13.01

2p 15.03

3s 8.68

3p 7.73

4s 3.50

Table 8.2

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 Splitting of Levels into Sublevels
• Each energy level is split into sublevels of differing energy.
– Splitting is caused by penetration and its effect on shielding.

• For a given n value, a lower l value indicates a lower energy

sublevel.
• Order of sublevel energies: s < p < d < f

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 Order for Filling Energy Sublevels With Electrons
• In general, energies of
sublevels increase as n
increases
– (1 < 2 < 3, etc.)

• and as l increases
– (s < p < d < f).

• As n increases, some
sublevels overlap.

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 Electron Configurations and Orbital Diagrams
• Electron Configurations:
• This shorthand notation consists of the principal energy level
(n value), the letter designation of the sublevel (l value), and
the number of electrons (#) in the sublevel, written as a
superscript:

• n: principle energy level

• l: sublevel (s/p/d/f)
• #: number of electrons

• An orbital diagram consists of a box (or just a line) for each

orbital in a given energy level, grouped by sublevel (with nl
designation shown beneath), with an arrow representing each
electron and its spin.
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 A Vertical Orbital Diagram for the Li Ground State

Figure 8.7

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 Building Orbital Diagrams:
Aufbau and Exclusion Principles
• The aufbau principle is applied – electrons are always placed
in the lowest energy sublevel available.
– H (Z = 1) 1s1

• The exclusion principle states that each orbital may contain a

maximum of 2 electrons, which must have opposite spins.
– He (Z = 2) 1s2

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 Building Orbital Diagrams:
Hund’s Rule
• Hund’s rule specifies that when orbitals of equal energy are
available, the lowest energy electron configuration has the
maximum number of unpaired electrons with parallel spins.
• N (Z = 7) 1s22s22p3

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 Sample Problem 8.1 - Problem and Plan
Correlating Quantum Numbers and Orbital Diagrams
• PROBLEM: Use the orbital diagram for fluorine to write sets of
quantum numbers for the third and eighth electrons of the F
atom.
• PLAN: Referring to the orbital diagram, we identify the
electron of interest and note its level (n), sublevel (l), orbital
(ml), and spin (ms).

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 Sample Problem 8.1 - Solution
• SOLUTION:
• The orbital diagram with the electrons of interest in red:

• The third electron is in the 2s orbital. Recall that l = 0 for an s

orbital. The upward arrow indicates a spin of + 1/2 :
– n = 2 , l = 0 , ml = 0 , ms = + 1/2

• The eighth electron is in the first 2p orbital (l = 1 for a p

orbital), which is designated ml = −1, and is represented by a
downward arrow because it was the second electron added to
that 2p orbital:
• n = 2 , l = 1 , ml = − 1 , ms = − 1/2

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 Depicting Orbital Occupancy for the First 10
Elements

Figure 8.8
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 Partial Orbital Diagrams and Condensed Configurations
• A partial orbital diagram shows only the highest energy
sublevels being filled.
– Al (Z = 13) 1s22s22p63s23p1

• A condensed electron configuration has the element symbol

of the previous noble gas in square brackets.
– Al has the condensed configuration [Ne]3s23p1

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 Electron Configuration and Group
• Elements in the same group of the periodic table have the
same outer electron configuration.
• Elements in the same group of the periodic table exhibit
similar chemical behavior.
• Similar outer electron configurations correlate with similar
chemical behavior.

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 Partial Orbital Diagrams and Electron Configurations
for the Elements in Period 3
Partial Orbital Diagram Full Electron Condensed Electron
Atomic Number Element (3s and 3p Sublevels Configuration† Configuration
Only)

11 Na [1s22s22p6] 3s1 [Ne] 3s1

12 Mg [1s22s22p6] 3s2 [Ne] 3s2

13 Al [1s22s22p6] 3s23p1 [Ne] 3s23p1

14 Si [1s22s22p6] 3s23p2 [Ne] 3s23p2

15 P [1s22s22p6] 3s23p3 [Ne] 3s23p3

16 S [1s22s22p6] 3s23p4 [Ne] 3s23p4

17 Cl [1s22s22p6] 3s23p5 [Ne] 3s23p5

18 Ar [1s22s22p6] 3s23p6 [Ne] 3s23p6

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 Partial Orbital Diagrams and Electron Configurations for the
Elements in Period 4
Partial Orbital Diagram (4s, 3d, and 4p Condensed Electron
Atomic Number Element Full Electron Configuration
Sublevels Only) Configuration

19 K 1s22s22p63s23p64s1 [Ar] 4s1

20 Ca 1s22s22p63s23p64s2 [Ar] 4s2
21 Sc 1s22s22p63s23p64s23d1 [Ar] 4s23d1
22 Ti 1s22s22p63s23p64s23d2 [Ar] 4s23d2
23 V 1s22s22p63s23p64s23d3 [Ar] 4s23d3
24 Cr 1s22s22p63s23p64s13d5 [Ar] 4s13d5
25 Mn 1s22s22p63s23p64s23d5 [Ar] 4s23d5
26 Fe 1s22s22p63s23p64s23d6 [Ar] 4s23d6
27 Co 1s22s22p63s23p64s23d7 [Ar] 4s23d7
28 Ni 1s22s22p63s23p64s23d8 [Ar] 4s23d8
29 Cu 1s22s22p63s23p64s13d10 [Ar] 4s13d10
30 Zn 1s22s22p63s23p64s23d10 [Ar]4s23d10
31 Ga 1s22s22p63s23p64s23d104p1 [Ar] 4s23d104p1
32 Ge 1s22s22p63s23p64s23d104p2 [Ar] 4s23d104p2
33 As 1s22s22p63s23p64s23d104p3 [Ar] 4s23d104p3
34 Se 1s22s22p63s23p64s23d104p4 [Ar] 4s23d104p4
35 Br 1s22s22p63s23p64s23d104p5 [Ar] 4s23d104p5
36 Kr 1s22s22p63s23p64s23d104p6 [Ar] 4s23d104p6

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 A Periodic Table of Partial Ground-state Electron Configurations

Figure 8.9
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 Orbital Filling and the Periodic Table
• The order in which the orbitals are filled can be obtained
directly from the periodic table.

Figure 8.10
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 Aid to Memorizing Sublevel Filling Order
• The n value is constant
horizontally.
• The l value is constant
vertically.
• n + l is constant
diagonally.

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 Categories of Electrons
• Inner (core) electrons are those an atom has in common with
the previous noble gas and any completed transition series.
• Outer electrons are those in the highest energy level (highest
n value).
• Valence electrons are those involved in forming
compounds.
– For main group elements, the valence electrons are the outer
electrons.
– For transition elements, the valence electrons include the outer
electrons and any (n -1)d electrons.

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 Similar Reactivities in a Group

Figure 8.11
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 Sample Problem 8.2 - Problem and Plan
Determining Electron Configurations
• PROBLEM: Using only the periodic table and assuming a regular filling
pattern, give the full and condensed electron configurations, partial orbital
diagram showing valence electrons only, and number of inner electrons
for the following elements:
a) Potassium (K; Z = 19)
b) Technetium (Tc; Z = 43)
c) Lead (Pb; Z = 82)

• PLAN: The atomic number tells us the number of electrons, and the
periodic table shows the order for filling sublevels. In the partial orbital
diagrams, we include all electrons added after the previous noble
gas except those in filled inner sublevels. The number of inner electrons is
the sum of those in the previous noble gas and in filled d and f sublevels.

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 Sample Problem 8.2 - Solution (a)
• SOLUTION (a):
• For K (Z = 19), the full electron configuration is
1s22s22p63s23p64s1.
• The condensed configuration is [Ar] 4s1.
• The partial orbital diagram showing valence electrons is:

• The inner electrons in K are those in the [Ar] part of the

condensed electron configuration.
• There are 18 inner electrons.

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 Sample Problem 8.2 - Solution (b)
• SOLUTION (b):
• For Tc (Z = 43), assuming the expected pattern, the full
electron configuration is 1s22s22p63s23p64s23d104p65s24d5.
• The condensed configuration is [Kr] 5s24d5.
• The partial orbital diagram showing valence electrons is:

• The inner electrons in Tc are those in the [Kr] part of the

condensed electron configuration.
• There are 36 inner electrons.

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 Sample Problem 8.2 - Solution (c)
• SOLUTION (c):
• For Pb (Z = 82), the full electron configuration is
1s22s22p63s23p64s23d104p65s2 4d105p66s24f145d106p2.
• The condensed configuration is [Xe] 6s24f145d106p2.
• The partial orbital diagram showing valence electrons is:

• The inner electrons in Pb are the 54 electrons represented by

[Xe] plus the 14 electrons in the filled 4f sublevel plus the 10
electrons in the filled 5d sublevel.
• There are 78 inner electrons.

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 Defining Atomic Size
• The metallic radius of aluminum.

• The covalent radius of chlorine.

• Known covalent radii and distances

between nuclei can be used to find
unknown radii.
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 Trends in Atomic Size
• Atomic size increases as the principal quantum number
n increases.
– As n increases, the probability that the outer electrons will be
farther from the nucleus increases.

• Atomic size decreases as the effective nuclear charge Zeff

increases.
– As Zeff increases, the outer electrons are pulled closer to the nucleus.

• For main group elements:

– atomic size increases down a group in the periodic table and
decreases across a period.

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 Atomic Radii of the Main-group and Transition Elements

Figure 8.13
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 Sample Problem 8.3 - Problem and Plan
Ranking Elements by Atomic Size
• PROBLEM: Using only the periodic table, rank each set of main-
group elements in order of decreasing atomic size:
a) Ca, Mg, Sr
b) K, Ga, Ca
c) Br, Rb, Kr
d) Sr, Ca, Rb
• PLAN: To rank the elements by atomic size, we find them in the
periodic table. They are main-group elements, so size
increases down a group and decreases across a period.

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 Sample Problem 8.3 - Solution
SOLUTION:
a) Sr > Ca > Mg. These three elements are in Group 2A(2), and
size increases down the group.
b) K > Ca > Ga. These three elements are in Period 4, and size
decreases across a period.
c) Rb > Br > Kr. Rb is largest because it has one more energy
level (Period 5) and is farthest to the left. Kr is smaller than
Br because Kr is farther to the right in Period 4.
d) Rb > Sr > Ca. Ca is smallest because it has one fewer energy
level. Sr is smaller than Rb because it is farther to the right.

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 Periodicity of Atomic Radius

Figure 8.14
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 Trends in Ionization Energy
• Ionization energy (IE) is the energy required for the complete
removal of 1 mol of electrons from 1 mol of gaseous atoms or
ions.
• Atoms with a low IE tend to form cations.
• Atoms with a high IE tend to form anions (except the noble
gases).
• Ionization energy tends to decrease down a group and
increase across a period.

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 Periodicity of First Ionization Energy (IE1)

Figure 8.15
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 First Ionization Energies of the Main-group Elements

Figure 8.16
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 Sample Problem 8.4 - Problem and Plan
Ranking Elements by Atomic Size
• PROBLEM: Using the periodic table only, rank the elements in
each set in order of decreasing IE1:
a) Kr, He, Ar
b) Sb, Te, Sn
c) K, Ca, Rb
d) I, Xe, Cs
• PLAN: We find the elements in the periodic table and then
apply the general trends of decreasing IE1 down a group and
increasing IE1across a period.

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 Sample Problem 8.4 - Solution
SOLUTION:
a) He > Ar > Kr. These are in Group 8A(18), and IE1decreases
down a group.
b) Te > Sb > Sn. These are in Period 5, and IE1 increases across a
period.
c) Ca > K > Rb. IE1 of K is larger than IE1 of Rb because K is
higher in Group 1A(1). IE1 of Ca is larger than IE1 of K because
Ca is farther to the right in Period 4.
d) Xe > I > Cs. IE1 of I is smaller than IE1 of Xe because I is farther
to the left. IE1 of I is larger than IE1 of Cs because I is farther
to the right and in the previous period.

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 The First Three Ionization Energies of Beryllium

Figure 8.17
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 Successive Ionization Energies of the Elements Lithium
Through Sodium
Ionization Energy (MJ/mol)
Number of
Valence
Z Element Electrons IE1 IE2 IE3 IE4 IE5 IE6 IE7 IE8 IE9 IE10

3 Li 1 0.52 7.30 11.81

CORE
4 Be 2 0.90 1.76 14.85 21.01 ELECTRONS

5 B 3 0.80 2.43 3.66 25.02 32.82

6 C 4 1.09 2.35 4.62 6.22 37.83 47.28

7 N 5 1.40 2.86 4.58 7.48 9.44 53.27 64.36

8 O 6 1.31 3.39 5.30 7.47 10.98 13.33 71.33 84.08

9 F 7 1.68 3.37 6.05 8.41 11.02 15.16 17.87 92.04 106.43

10 Ne 8 2.08 3.95 6.12 9.37 12.18 15.24 20.00 23.07 115.38 131.43

11 Na 1 0.50 4.56 6.91 9.54 13.35 16.61 20.11 25.49 28.93 141.37

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 Sample Problem 8.5 - Problem and Plan
Ranking Elements by Atomic Size
• PROBLEM: Name the Period 3 element with the following
ionization energies (kJ/mol), and write its full electron
configuration:
IE1 IE2 IE3 IE4 IE5 IE6
1012 1903 2910 4956 6278 22,230

• PLAN: We look for a large jump in the IE values, which occurs

after all valence electrons have been removed. Then we refer
to the periodic table to find the Period 3 element with this
number of valence electrons and write its electron
configuration.

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 Sample Problem 8.5 - Solution
SOLUTION:
• The large jump occurs after IE5, indicating that the element
has five valence electrons and, thus, is in Group 5A(15).
This Period 3 element is phosphorus (P; Z = 15). Its full
electron configuration is 1s22s22p63s23p3.

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 Trends in Electron Affinity
• Electron Affinity (EA) is the energy change that occurs when 1
mol of electrons is added to 1 mol of gaseous atoms or ions.
• Atoms with a low EA tend to form cations.
• Atoms with a high EA tend to form anions.
• The trends in electron affinity are not as regular as those for
atomic size or IE.

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 Electron Affinities of the Main-group Elements (In Kj/Mol)

Figure 8.18
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 Behavior Patterns for IE and EA
• Reactive nonmetals have high IEs and highly negative
EAs.
– These elements attract electrons strongly and tend to form
negative ions in ionic compounds.
• Reactive metals have low IEs and slightly negative EAs.
– These elements lose electrons easily and tend to form positive
ions in ionic compounds.
• Noble gases have very high IEs and slightly positive EAs.
– These elements tend to neither lose nor gain electrons.

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 Trends in Three Atomic Properties

Figure 8.19
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 Metallic Behavior
• Metals are typically shiny solids with moderate to high
melting points.
• Metals are good conductors of heat and electricity, and
can easily be shaped.
• Metals tend to lose electrons and form cations, i.e., they
are easily oxidized.
• Metals are generally strong reducing agents.

• Most metals form ionic oxides, which are basic in

aqueous solution.

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 Trends in Metallic Behavior

Figure 8.20
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 Metallic Behavior in Group 5A(15) and Period 3

• Metallic behavior decreases across the period.

• Metallic behavior increases down the group.

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 Highest And Lowest O.N.S of Reactive Main-group Elements

Figure 8.22
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 Oxide Acidity
• CaO, the oxide of a main-group metal, is strongly basic.
• P4O10, the oxide of a main-group nonmetal, is acidic.

Figure 8.23

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 Acid-Base Behavior of Oxides
• Main-group metals form ionic oxides, which are basic in
aqueous solution.
• Main-group nonmetals form covalent oxides, which are acidic
in aqueous solution.
• Some metals and metalloids from amphoteric oxides, which
can act as acids or bases in water:
• Al2O3 (s) + 6HCl (aq) → 2AlCl3 (aq) + 3H2O (l)
• Al2O3 (s) + 2NaOH (aq) + 3H2O (l) → 2NaAl(OH)4 (aq)

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 Acid-base Behavior of Some Element Oxides
• Oxides become more basic down a group and more acidic
across a period.

Figure 8.24
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 Electron Configurations of Monatomic Ions
• Elements at either end of a period gain or lose electrons to
attain a filled outer level. The resulting ion will have a noble
gas electron configuration and is said to be isoelectronic with
that noble gas.
• Na(1s22s22p63s1) → e– + Na+([He]2s22p6)
[isoelectronic with Ne]
• Br([Ar]4s23d104p5) + e– → Br- ([Ar]4s23d104p6)
[isoelectronic with Kr]

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 Main-group Elements Whose Ions Have Noble Gas
Electron Configurations

Figure 8.25
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 Electron Configurations of Monatomic Ions
• A pseudo-noble gas configuration is attained when a metal
atom empties its highest energy level.
– The ion attains the stability of empty ns and np sublevels and a filled (n
– 1)d sublevel.
– Sn ([Kr]5s24d105p2) → 4e– + Sn4+ ([Kr]4d10)

• A metal may lose only the np electrons to attain an inert pair

configuration.
– The ion attains the stability of a filled ns and (n – 1)d sublevels.
– Sn([Kr]5s24d105p2) → 2e– + Sn2+ ([Kr]5s24d10)

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 Sample Problem 8.6 - Problem and Plan
Writing Electron Configurations of Main-Group Ions
• Using condensed electron configurations, write equations
representing the formation of the ion(s) of the following
elements:
a) Iodine (Z = 53)
b) Potassium (Z = 19)
c) Indium (Z = 49)
• PLAN: We identify the element’s position in the periodic table
and recall that:
– Ions of elements in Groups 1A(1), 2A(2), 6A(16), and 7A(17)are
isoelectronic with the nearest noble gas.
– Metals in Groups 3A(13) to 5A(15) lose the ns and np electrons or just
the np.
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 Sample Problem 8.6: Solution
SOLUTION:
a) Iodine is in Group 7A(17), so it gains one electron, and I−is
isoelectronic with xenon:
I ([Kr] 5s24d105p5) + e– → I– ([Kr] 5s24d105p6)

b) Potassium is in Group 1A(1), so it loses one electron; K+ is

isoelectronic with argon:
K ([Ar] 4s1) → K+ ([Ar]) + e–

c) Indium is in Group 3A(13), so it loses either three electrons

to form In3+ (with a pseudo–noble gas configuration) or one
to form In+ (with an inert pair):
In ([Kr] 5s24d105p1) → In+ ([Kr] 5s24d10) + e–
In ([Kr] 5s24d105p1) → In3+([Kr] 4d10) + 3e–

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 The Crossover of Sublevel Energies in Period 4

Figure 8.26
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 Magnetic Properties of Transition Metal ions
• A species with one or more unpaired electrons exhibits
paramagnetism – it is attracted by a magnetic field.
– Ag (Z=47) [Kr] 5s14d10

• A species with all its electrons paired exhibits diamagnetism –

it is not attracted (and is slightly repelled) by a magnetic field.

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 Measuring the Magnetic Behavior of a Sample
• The apparent mass of a
diamagnetic substance is
unaffected by the magnetic
field.

• The apparent mass of a

paramagnetic substance
increases as it is attracted
by the magnetic field.

Figure 8.27

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 Sample Problem 8.7 - Problem and Plan
Writing Electron Configurations and Predicting Magnetic
Behavior of Transition Metal Ions
• PROBLEM: Use condensed electron configurations to write an
equation for the formation of each transition metal ion, and
predict whether it is paramagnetic:
a) Co3+ (Z = 27)
b) Cr3+ (Z = 24)
c) Hg2+ (Z = 80)
• PLAN: We first write the condensed electron configuration of
the atom, recalling the irregularity for Cr. Then we remove
electrons, beginning with ns electrons, to attain the ion
charge. If unpaired electrons are present, the ion is
paramagnetic.
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 Sample Problem 8.7 - Solution
SOLUTION:
a) Co3+(Z = 27) Co ([Ar] 4s23d7) → Co3+ ([Ar] 3d6) + 3e−
There are four unpaired e−, so Co3+ is paramagnetic.

b) Cr3+(Z = 24) Cr ([Ar] 4s13d5) → Cr3+ ([Ar] 3d3) + 3e−

There are three unpaired e−, so Cr3+ is paramagnetic.

c) Hg2+(Z = 80) Hg ([Xe] 6s24f145d10) → Hg2+ ([Xe] 4f145d10) + 2e−

The 4f and 5d sublevels are filled, so there are no

unpaired e−: Hg2+ is not paramagnetic.

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 Ionic Size vs. Atomic Size
• Cations are smaller than their parent atoms while anions are
larger.
• Ionic radius increases down a group as n increases.
• Cation size decreases as charge increases.
• An isoelectronic series is a series of ions that have the same
electron configuration. Within the series, ion size decreases
with increasing nuclear charge:
3– > 2– > 1– > 1+ > 2+ > 3+

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 Ionic Radius

Figure 8.28
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 Ionic vs. Atomic Radii

Figure 8.29
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 Sample Problem 8.8 - Problem and Plan
Ranking Ions by Size
• PROBLEM: Rank each set of ions in order of decreasing size, and
explain your ranking:
a) Ca2+, Sr2+, Mg2+
b) K+, S2−, Cl−
c) Au+, Au3+
• PLAN: We find the position of each element in the periodic
table and apply the ideas presented in the text.

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 Sample Problem 8.8 - Solution
SOLUTION:
a) Mg2+, Ca2+, and Sr2+ are all from Group 2A(2), so their sizes
decrease up the group: Sr2+ > Ca2+ > Mg2+.
b) The ions K+, S2−, and Cl− are isoelectronic. S2− has a
lower Zeff than Cl−, so it is larger. K+ is a cation and has the
highest Zeff, so it is smallest: S2− > Cl− > K+.
c) Au+ has a lower charge than Au3+, so it is larger: Au+ > Au3+.

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