GENERAL CHEMISTRY

Principles and Modern Applications 8 th EDITION

Petrucci • Harwood • Herring

Chapter 9: The Periodic Table and Some

Atomic Properties

9
1
The Periodic Table and
Some Atomic Properties

CONTENTS

9-1 Classifying the Elements: The Periodic Law and the

Periodic Table

9-2 Metals and Nonmetals and Their Ions

9-3 Sizes of Atoms and Ions
9-4 Ionization Energy

9-5 Electron Affinity

9-6 Magnetic Properties

9-7 Periodic Properties of the Elements

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9-1 Classifying the Elements:
The Periodic Law and the Periodic Table

1869 Dimitri Mendeleev

Lothar Meyer
Proposed the periodic law:

When the elements are arranged in order of increasing atomic mass, certain sets of
properties recur periodically.

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Periodic law: refers to the periodic recurrence of certain physical and chemical
properties when the elements are considered in terms of increasing atomic number.

• An adaptation of Lothar Meyer’s 1870 plot

of atomic volume against atomic number.
• Alkali metals lie on the peaks.
• Non-metals fall on the ascending portions.
• Metals are present on the descending slopes
and in the valleys.

An illustration of the periodic law – variation

of atomic volume with atomic number

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 • Mendeleev’s work attracted more attention than Meyer’s for two reasons:
1. Mendeleev left blank spaces in his table, at 44, 68, 72, and 100, for undiscovered
elements (Sc, Ga, Ge and Tc).
2. He corrected some atomic mass values (In, U).

Mendeleev’s Periodic Table

— = 44
— = 68 — = 72
— = 100

Mendeleev discovered
Galium (1875) and Scandium (1879).

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Atomic Number as the Basis for the Periodic Law

Moseley 1913
• X-ray emission is explained in terms of transitions in
which e- drop into orbits close to the atomic nucleus.
• Correlated frequencies to nuclear charges.

n = A (Z – b)2
• Where n is the X-ray frequency , Z is the atomic
number, and A and b are constants.
• Used to predict new elements (43, 61, 75) later
discovered.

Schematic of an X-ray tube and Moseley’s

X-ray spectra of several elements

When the elements are arranged according to increasing atomic number, similar 6
properties recur periodically.
Alkali Metals The Periodic table Noble Gases

Alkaline Earths Main Group

Halogens

Transition Metals

Main Group Lanthanides and Actinides

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9-2 Metals and Nonmetals and Their Ions

• Metals
Good conductors of heat and electricity.
Malleable and ductile.
Moderate to high melting points.

• Nonmetals
Nonconductors of heat and electricity.
Brittle solids.
Some are gases at room temperature.

• Metalloids
Metallic and non-metallic properties

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• Main-Group Metal Ions

Metals tend to lose electrons to attain noble gas electron configurations.

Li ([He]2s1) → Li+ ([He]) + e-

Ca ([Ar]4s2) → Ca2+ ([Ar]) + 2e-

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• Main-Group Nonmetal Ions

Nonmetals tend to gain electrons to attain noble-gas electron configurations.

O ([He]3s23p4) + 2e- → O2- ([Ne])

Cl ([Ne]3s23p5) + e- → Cl- ([Ar])

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• Transition Metal Ions
Ø e- are lost from the ns subshell before the (n-1)d subshell, even though the ns
subshell is lower in energy.

Ø Electrons can be lost from both the ns and the (n-1)d subshells in an ionization
process.

Ø In losing electrons, some T.M. ions acquire noble gas configuration

Ti ([Ar]3d24s2) → Ti4+ ([Ar]) + 4e-

Ø However, some T.M. ions do not

Fe([Ar]3d64s2 → Fe2+ ([Ar]3d6) + 2e-

Ø And certain elements can form ions with different charges:

Fe([Ar]3d64s2 → Fe3+ ([Ar]3d5) + 3e-

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9-3 Sizes of Atoms and Ions

• Atomic radius
Difficult to define since the probability of finding an electron decreases with
increasing distance from the nucleus, but nowhere does the probability fall to zero.
– Atomic radius is therefore defined in terms of internuclear distance.

• Covalent radius
One half the distance between the centers of two atoms that are bonded covalently.
It is the atomic radius associated with an element in its covalent compounds.

Na2(g) – Covalent Na2 is found only in gaseous sodium.

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• Ionic radius
The radius of a spherical ion. It is the atomic radius associated with an element in its
ionic compounds.

Na+ – Cationic radius of sodium is obtained by

comparison to other ionic compounds containing the
anionic component.

• Metallic radius
One half the distance between the centers of adjacent atoms in a solid metal.

Na (s) – Adjacent centers in metallic sodium

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Screening
• Screening (shielding): reflects how an outer electron is blocked from the nuclear charge
by inner electrons.
• Effective nuclear charge (Zeff): Zeff = Z – S
Z is atomic number
S is “shielding constant”
number of inner e

The shielding effect and effective nuclear charge, Zeff

• Two valence electrons attracted to the +12 nucleus of a Mg atom (12 e-).
• The nuclear charge is screened by the 10 core electrons, but not perfectly.
Zeff2
• Valence electrons also screen each other somewhat. En = - RH
• Zeff is therefore closer to +3 than to +2.
n2 15
Screening and Penetration
Atomic radii

• Graph showing the metallic radii for metals and covalent radii for nonmentals.
• Radii increase down a group.
• Radii decrease across a period in the main group (Zeff increases across main group elements).
• Radii in Transition metals remain fairly constant except for a few spikes.

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• The more electronic shells in an atom, the larger is the atom. Atomic radius
increases from top to bottom through a group of elements.

• The atomic radius decreases from left to right through a period of elements.

Increasing Size

Increasing Size
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Ionic Radius
• When a metal atom loses one or more electrons to form a positive ion, the nuclear charge
exceeds the negative charge of the electrons in the resulting ion.

• The nucleus draws the remaining electrons in closer. Cations are therefore smaller than their
parent atoms.

• Na+ and Mg 2+ are isoelectronic, but Mg 2+ is smaller because its nuclear charge is larger.

A comparison of atomic and ionic sizes

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• When a non-metal atom gains one or more electrons to form a negative ion, the nuclear
charge remains constant, but Zeff is reduced because of the additional electrons.

• Electrons are held more loosely.

• Inter-electron (a.k.a. electron electron, e--e-) repulsions increase.

• The electrons spread out more, and the size of the atom increases.

Covalent and anionic radii compared

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Ionic Radius

Cations are smaller than the atoms from which they are formed.

For isoelectronic cations, the more positive the ionic charge, the smaller
the ionic radius.

Anions are larger than the atoms from which they are formed. For isoelectronic
anions, the more negative the charge, the larger the ionic radius.

For isoelectronic anions, the more negative the charge, the larger the ionic radius.

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A comparison of some atomic and ionic radii

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9-4 Ionization Energy
• Ionization energy is the quantity of energy a gaseous atom must absorb so that an
electron is stripped from it. The electron lost is the one most loosely held (in the highest
energy orbital, i.e. the valence electrons).

• The ionization energy, I = -E, where E is the energy of the electron on the orbital shell, n.

• As n increases, I decreases.

Zeff2
I = RH 2
n

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• It is more difficult to pull off a second electron from the nucleus.
Positive charge of the ion wants to attract the remaining electrons.

• First Ionization Energy (I1): is the energy required to remove the most loosely held
electron from a gaseous atom.

• Second Ionization Energy (I2): is the energy required to remove an electron from a
gaseous, unipositve (+1) ion.

Mg(g) → Mg+(g) + e- I1 = 738 kJ

Mg+(g) → Mg2+(g) + e- I2 = 1451 kJ

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Ionization energies decrease as atomic radii increase.

Increasing Ionization Energy

Increasing Ionization Energy

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First ionization energies as a function of atomic number

• Noble gases are the most difficult to ionize.

• The maxima on the graph come at the atomic numbers of the noble gases.
• Alkali metals are the easiest to ionize.
• The minima in the graph come at the atomic numbers of the alkali metals.
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 577.6 1012 999.6
1451
7733

I2 (Mg) vs. I3 (Mg) I1 (Mg) vs. I1 (Al) I1 (P) vs. I1 (S)

• Once the valence electrons are lost, considerably more energy is required to remove
very stable core electrons.
• Removing the third electron from Mg causes a large jump in I.
• I1 of Al less than Mg because an s-electron is removed from Mg and a p-electron is
removed from Al.
• I1 of S is less than that of P. This is due to e--e- repulsion of the fourth p-electron.
([Ne]3s23p3 for P, [Ne]3s23p4 for S)
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9-5 Electron Affinity
• The energy change associated with the gain of an electron by a neutral gaseous ion.

• This is an exothermic process, but for second electron affinities it may be difficult to acquire
another electron.

F(g) + e- → F-(g) EA = -328 kJ

F(1s22s22p5) + e- → F-(1s22s22p6)

• Even metals can gain an electron in the gaseous state if no other metal atoms are nearby.

Li(g) + e- → Li-(g) EA = -59.6 kJ

Li(g) (1s22s1) + e- → Li-(g) (1s22s2)

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Second Electron Affinities

• Second electron affinity for O is endothermic.

• The gain of a second electron leads to strong repulsive forces between a
negatively charged ion and the incoming electron

O(g) + e- → O-(g) EA = -141 kJ

O-(g) + e- → O2-(g) EA = +744 kJ

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Electron affinities of main-group elements

Values are in kilojoules per mole for the process.

X(g) + e- → X-(g).

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9-6 Magnetic Properties

Diamagnetic atoms or ions:

All e- are paired.
Weakly repelled by a magnetic field.

Paramagnetic atoms or ions:

Unpaired e-.
Attracted to an external magnetic field.

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Paramagnetism

• Manganese metal has 5 upe.

• The Mn2+ ion has lost 2 electrons from the 4s orbital.

The Mn2+ still has 5 upe, all of which remain in the
3d orbital.

• Mn3+ has 4 upe. One of the 3d electrons is lost to

leave a 3d4 configuration in the valence orbital.

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9-7 Periodic Properties of the Elements

Atomic properties and the periodic table – a summary

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The value of a property often changes uniformly from the top to the bottom of a
group of elements in the periodic table.

266
? 332
?

Three halogen elements

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37
Melting points of the third-period elements

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Reducing Abilities of Group 1 and 2 Metals

2 K(s) + 2 H2O(l) → 2 K+ + 2 OH- + H2(g)

I1 = 419 kJ

Ca(s) + 2 H2O(l) → Ca2+ + 2 OH- + H2(g)

I1 = 590 kJ
I2 = 1145 kJ
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Oxidizing Abilities of the Halogen Elements (Group 17)

2 Na + Cl2 → 2 NaCl

Cl2 + 2 I- → 2 Cl- + I2

Cl has higher electron affinity than I, therefore the reaction should lie to the right.
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Acid-Base Nature of Element Oxides

• Basic oxides or base anhydrides:

Li2O(s) + H2O(l) → 2 Li+(aq) + 2 OH-(aq)

• Acidic oxides or acid anhydrides:

SO2 (g) + H2O(l) → H2SO3(aq)

Na2O and MgO yield basic solutions

Cl2O, SO2 and P4O10 yield acidic solutions
SiO2 dissolves in strong base, acidic oxide.

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End of Chapter Questions
Think of a problem like a root system:
Each branching is a decision.
The answer is at the tip of one of the rootlets.
a

c d

e f
g h Answer

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