Chapter 8 Notes

CHEM 1411 General Chemistry Chemistry: A Molecular Approach by Nivaldo J. Tro

Periodic Properties
8 of the Elements
Chapter Objectives:
• Learn how to write electron configurations for
neutral atoms and ions.
• Learn how to predict trends in atomic radius,
effective nuclear charge, ionic radius, ionization
energy, electron affinity, and metallic character
from the positions of the elements on the
periodic table.
Mr. Kevin A. Boudreaux
Angelo State University 1
www.angelo.edu/faculty/kboudrea

Periodic Properties
• A number of element and ion properties vary in a
periodic, predictable way across the periodic table.
These include:
– atomic radius
– effective nuclear charge
– ionic radius
– ionization energy
– electron affinity
– metallic character
– electronegativity (Ch. 9)

2
Chapter 8 Notes

The Development
of the
Periodic Table
3

Periodic Properties
• It has long been known that many of the elements
have similar chemical properties.
– Lithium, sodium, and potassium all perform the
same reaction with water,
2M(s) + 2HOH(l) → 2MOH(aq) + H2(g)
the only difference being the masses of the metals
themselves and the vigor and speed of the
reaction.

Lithium Sodium Potassium

slow fast warp speed 4
Chapter 8 Notes

The Invention of the Periodic Table

• In 1869 Dimitri Mendeleev published a table in
which the elements that were known at the time
were arranged by increasing atomic mass, and
grouped into columns according to their chemical
properties. The properties of the elements varied
(more or less) in a periodic way in this arrangement.

Atomic Sodium
Weight Chlorides Salts Mendeleev’s Periodic Table
H 1 HCl
Li
Be
7
9.4
LiCl
BeCl2
• Mendeleev noticed that when he
B 11 BCl3 grouped the elements by their
C
N
12
14
CCl4
Na3N
properties, there were some “holes”
O 16 Na2O which he guessed corresponded to
F
Na
19
23 NaCl
NaF as-yet-unknown elements.
Mg 24 MgCl2
Al 27.3 AlCl3 • Mendeleev predicted some of the
Si 28 SiCl4 properties for two of these, eka-
P 31 Na3P
S 32 Na2S aluminum (?=68), and eka-silicon
Cl 35.5 NaCl (?=72), which corresponded well to
K 39 KCl
Ca 40 CaCl2 gallium (Ga, discovered in 1875)
As 75 Na3As and germanium (Ge, 1886)
Se 78 Na2Se
Br 80 NaBr

6
Chapter 8 Notes

The Periodic Table by Atomic Number

• To make the properties of the elements “line up”
properly, it was sometimes necessary to exchange
the order of the elements.
– For instance, potassium (39.0983 g/mol) is slightly lighter than
argon (39.948 g/mol), so by increasing atomic weight,
potassium should be in Group 8A, and argon in Group 1A, but
that clearly doesn’t fit their observed properties.
• After the discovery of the nucleus and the proton,
and with the development of X-ray spectroscopy, it
was discovered that the periodic table could be
written in order of increasing atomic number, with
no need to “play around” with the order of the
elements. It was also possible to count protons, and
see exactly how many “missing” elements there
were.
7

The Modern Periodic Table of the Elements

8
Chapter 8 Notes

Electron
Configurations

Energy Levels of One-Electron Atoms

• In one-electron atoms (H, He+, etc.) the energy of
the orbital depends only on n. The 2s and 2p
orbitals have the same energy, the 3s, 3p, and 3d
orbitals all have the same energy, etc. (Orbitals
having the same energy are said to be degenerate.)

10
Chapter 8 Notes

Energy Levels of Multi-Electron Atoms

• In multi-electron atoms the orbital energy depends
on n and l (s<p<d<f), so there are differences in
energy between the subshells.

11

Energy Levels of Multi-Electron Atoms

• There is some crossover of energies from one shell
to another. (A 3d orbital in some atoms is higher in
energy than a 4s orbital.)
• These energy differences result from a balance of
attractive forces between electrons and the nucleus,
and repulsive forces between electrons.
• Adding more electrons increases electron-electron
repulsions.
• Having more protons in the nucleus lowers the
energy of close-lying electrons.
• Orbitals which have a greater electron density near
the nucleus experience more of the nuclear charge,
and are lowered in energy because of their greater
penetration of the inner atomic core.
12
Chapter 8 Notes

Energy Levels of Multi-Electron Atoms

• Repulsion of the outer-shell electrons by ones in
lower-lying shells cause the outer-shell electrons to
be pushed father away from the nucleus, and to be
held less tightly. Part of their attraction for the
nucleus is canceled, and we say that these electrons
are shielded from the nucleus by the inner electrons.

13
Figure 8.4

Putting Everything Together

• Knowing the relative energies of the
various orbitals allows us to predict the
electron configuration for any atom or
ion — a list of how the electrons in that
atom are distributed among its orbitals.
• Each successive electron added to an
atom occupies the lowest-energy orbital
available, resulting in the ground-state
configuration of the atom.
• A set of rules called the aufbau
principle (German, building-up) guides
the order in which orbitals are filled.

14
Chapter 8 Notes

The Aufbau Principle

• Lower-energy orbitals fill before higher-energy
orbitals. The order in which the orbitals are filled is:
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p,
6s, 4f, 5d, 6p, 7s, 5f
• An orbital can hold only two electrons, which must
have opposite spins (Pauli exclusion principle).
• Hund’s Rule: If two or more degenerate orbitals
(orbital at the same energy level) are available, one
electron goes into each orbital (spin up) until all are
half-full; only then does a second electron fill one of
the orbitals. (This is a consequence of the mutual
repulsion between like charged-electrons.)
15

Writing Electron Configurations

• To write an element’s electron configuration, write
in the orbitals that are occupied by electrons,
followed by a superscript to indicate how many
electrons are in the set of orbitals (e.g., H 1s1)
• Another way to show the placement of electrons is
an orbital diagram, in which each orbital is
represented by a circle (or a line, or a square), and
the electrons as arrows pointing up (↑) or down (↓)
(indicating the electron spin).

16
Chapter 8 Notes

Examples: Electron Configurations

1. Using the diagram on the next page, write the
electron configuration and orbital diagram for the
following elements, and state whether they are
diamagnetic or paramagnetic.
Li 1s22s1
Be 1s22s2
B 1s22s22p1
C
N
O
F
Ne 17

18
Chapter 8 Notes

Abbreviated Electron Configurations

• For atoms following neon, the full electron
configuration can be extremely cumbersome to
write:
Ba: 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 5s2 5p6 6s2
• Since everything up to the 5p6 is exactly the same
electron configuration as the noble gas xenon (Xe),
this configuration can be abbreviated as:
Ba: [Xe] 6s2
• Abbreviated electron configurations are always
based on the nearest preceding noble gas.

19

Electron Configurations and the Periodic Table

• It is not necessary to memorize the orbital order in
the aufbau scheme, because this sequence can be
read from the periodic table in the following fashion:

20
Chapter 8 Notes

Electron Configurations and the Periodic Table

1s 1s

n (n)s (n)p
(n-1)d

(n-2)f 21

Examples: Electron Configurations

2. For the following elements, provide the abbreviated
electron configuration, orbital diagram, and state
whether the element is diamagnetic or paramagnetic.
Na
Mg
Al
Cl
Ar
Fe
Sn
Pb
I 22
Chapter 8 Notes

Valence Electrons
• Valence electrons are the electrons in the outermost
shell (with the highest value of n). All the elements
in the same group on the periodic table have similar
electron configurations for their valence shells, and
therefore have similar chemical properties.
• Core electrons are those in complete principal
energy levels, and do not participate in bonding.

Fig.
23
8.6

Periodic Table of Valence Shell Configurations

24
Figure 8.7
Chapter 8 Notes

Some Anomalous Electron Configurations

• Half-filled and filled subshells have special stability,
leading to some unexpected electron configurations:
– Cr [Ar]3d44s2 actual: [Ar]3d54s1
– Cu [Ar]3d94s2 actual: [Ar]3d104s1
– Ag [Kr]4d95s2 actual: [Kr]4d105s1
– Au [Xe]4f145d96s2 actual: [Xe]4f145d106s1
• Most of the anomalous electron configurations occur
in elements with atomic numbers greater than Z =
40, where the energy differences between subshells
are very small. In all of these cases, the transfer of
an electron from one subshell to another lowers the
total energy of the atom because of a decrease in
electron-electron repulsion.
25

The Explanatory Power of the QM Model

• The chemical properties of elements are largely
determined by the number of valence electrons they
contain.
– The Group 8A elements are inert because their
valence shells are already full.
– The Group 1A elements (ns1) can attain a noble
gas configuration by losing their single valence
electrons, forming 1+ charges.
– The Group 2A elements (ns2) lose their two
valence electrons to form 2+ charges.
– The Group 7A elements (ns2np5) gain one
electron to complete their valence shells.

26
Chapter 8 Notes

Atomic Radius
and
Effective Nuclear
Charge
27

Atomic Radius
• The atomic radius of an atom can be measured
either by taking one-half of the distance between
atoms in an atomic solid (the nonbonding atomic
radius or van der Waals radius) or by taking one
half of the distance between two identical bonded
nuclei or between atoms in a metallic crystal (the
bonding atomic radius or covalent radius).

28
Chapter 8 Notes

Trends in Atomic Radii

• An average atomic radius for a particular element
can be determined from the measurement of a large
number of elements and compounds.
• When the atomic radius is graphed against the
atomic number (Figures 8.9 and 8.10), there is a
periodic pattern to the radii across a group:
– the radius is largest for the Group 1A elements,
and becomes smaller as we move towards the
Group 8A elements.
– for elements in a particular group, the size
increases from top to bottom within the group.

29

Trends in Atomic Radii

30
Figure 8.9
Chapter 8 Notes

Atomic Radius: Top to Bottom

• As we add larger valence shells (larger values of n),
the size of the atom increases. Therefore, atomic
size increases as we move from top to bottom in a
group.

31

Effective Nuclear Charge

• The net nuclear charge actually felt by an outer-shell
electron, called the effective nuclear charge (Zeff),
is often substantially lower than the actual nuclear
charge Z, because the core electrons “shield” the
outer electrons from the full effect of the nuclear
charge:
Zeff = Zactual - Electron shielding

32
Figure 8.11
Chapter 8 Notes

Atomic Radius: Left to Right

• As we move to the right in a period, there are more
protons in the nucleus, but no increase in shielding
(the number of inner electrons isn’t changing, and
valence electrons don’t shield each other). Zeff
increases from left to right across a period.
valence electrons
inner electrons
nucleus

• An increasing Zeff means there is a stronger

attraction between the nucleus and the valence
electrons. Therefore, atomic radius decreases from
left to right in a period.
33

Trends in Atomic Radii

34
Figure 8.10
Chapter 8 Notes

Effective Nuclear Charge and Atomic Radius

35

Examples: Atomic Radii and the Size of Atoms

3. Which atom is larger, C or N?

4. Which atom is larger, Si or Ge?

5. Which atom is larger, Mg or Ba?

6. Which atom is larger, Al or Ge?

7. Arrange the following elements in order of

increasing size: Cs, Rb, Sr, Ca.
36
Chapter 8 Notes

Properties of Ions

37

The Valence Shell

• The electrons in the outermost or valence shell (the
one that has the highest value of n) have the highest
energies, and are on average the farthest away from
the nucleus, and so are the ones which are most
exposed to other atoms.
– For main-group metals, the electrons lost in
forming cations are taken from the valence shell.
– For main-group nonmetals, the electrons gained
in forming anions are added to the valence shell.
• The inner, core electrons (inner shell) do not usually
play a role in chemical bonding.

38
Chapter 8 Notes

The Formation of Sodium Chloride

• When sodium reacts with chlorine, the 3s1 electron
in sodium is lost, producing an sodium ion :
Na 1s22s22p63s1 → Na+ 1s22s22p6 + e-
– The next shell down (n=2) is now the outermost
shell, which is full; there is little tendency to lose
more electrons.
– The Na+ ion has the same configuration as the
noble gas neon, with 8 e-’s in the valence shell.
• The chlorine atom accepts an electron into its 3p
subshell, filling the n=3 shell:
Cl 1s22s22p63s23p5 + e- → Cl- 1s22s22p63s23p6
– The Cl- ion the same electron configuration as the
noble gas argon, with 8 e-’s in the valence shell.
39
MOV: Formation of Sodium Chloride

The Octet Rule

• The Na+ and Cl- ion’s electron configurations are the
same as that of the nearest noble gas (the ions are
said to be isoelectronic with the nearest noble gas).
Atoms “prefer” to have a filled outermost shell
because this is more electronically stable.
• This can be generalized into the octet rule: Main-
group elements tend to undergo reactions that leave
them with eight outer-shell electrons.
– That is, main-group elements react so that they
attain a noble gas e- configuration with filled s
and p sublevels in their valence electron shell.
• There are many exceptions to the octet rule, but it is
useful for making predictions about some chemical
bonds.
40
Chapter 8 Notes

Group 1A-3A Cations

• Elements with similar outer shell configurations
form similar ions.
• For instance, the alkali metals form ions with a +1
charge; the valence s1 electron is the one that’s lost:
1A Li 1s22s1 Li+ 1s2
1A Na 1s22s22p63s1 Na+ 1s22s22p6
1A K 1s22s22p63s23p64s1 K+ 1s22s22p63s23p6
• The Group 2A and 3A metals also tend to lose all of
their valence electrons to form cations.
2A Be 1s22s2 Be2+ 1s2
2A Mg 1s22s22p63s2 Mg2+ 1s22s22p6
3A Al 1s22s22p63s23p1 Al3+ 1s22s22p6
41

Group 4A and 5A Cations

• The Group IV and V metals can lose either the
electrons from the p subshell, or from both the s and
p subshells, thus attaining a pseudo-noble gas
configuration.
4A Sn [Kr]4d105s25p2
Sn2+ [Kr]4d105s2
Sn4+ [Kr]4d10
4A Pb [Xe]4f145d106s26p2
Pb2+ [Xe]4f145d106s2
Pb4+ [Xe]4f145d10
5A Bi [Xe]4f145d106s26p3
Bi3+ [Xe]4f145d106s2
Bi5+ [Xe]4f145d10 42
Chapter 8 Notes

Transition Metal Cations

• Transition metals lose their ns electrons before the
(n-1)d electrons, usually forming 2+ charges. Some
can also lose electrons from their highest d levels.
Fe [Ar] 3d64s2
Fe2+ [Ar] 3d6
Fe3+ [Ar] 3d5
——————————————————————
Zn [Ar] 3d10 4s2
Zn2+ [Ar] 3d10
——————————————————————
Ag [Kr] 4d10 5s1
Ag+ [Kr] 4d10
43

Nonmetal Anions and Noble Gases

• The Group 6A – 8A non-metals gain electrons until
their valence shells are full (8 electrons).
4A C 1s22s22p2 C4- 1s22s22p6
5A N 1s22s22p3 N3- 1s22s22p6
6A O 1s22s22p4 O2- 1s22s22p6
7A F 1s22s22p5 F- 1s22s22p6
• The Group 8A noble gases already possess a full
outer shell, so they have no tendency to form ions.
8A Ne 1s22s22p6
8A Ar 1s22s22p63s23p6

44
Chapter 8 Notes

Examples: Predicting Ion Configurations

8. Predict the ground-state electron configuration for
each of the following ions, and state whether they
are diamagnetic or paramagnetic. (sim. to Ex. 8.6)
a. Ra2+
b. La2+ , La3+
c. Mn2+, Mn3+
d. Ni2+
e. Ti4+
f. N3-
g. Te2-
45

Examples: Predicting Ion Configurations

9. What 2+ ion has the ground-state electron
configuration 1s22s22p63s23p63d10 ?

46
Chapter 8 Notes

Ionic Radii
• Cations are smaller than their parent atoms, since
electrons are being removed from the valence shell.
• Anions are larger than their parent atoms, since the
number of electron-electron repulsions increases
when electrons are added.
• The greater the ionic charge, the smaller the ionic
radius (e.g., Fe3+ < Fe2+).
• Trends in ion size are the same as for neutral atoms:
– Ionic size increases down a group.
– Ionic size decreases for cations across a period.
– Ionic size decreases for anions across a period.

47
MOV: Gain and Loss of Electrons

←Figure
8.12

Figure→
8.13

48
Chapter 8 Notes

Examples: Predicting Periodic Trends

10. Arrange the following ions in order of increasing
size: O2-, P3-, S2-, As3-.

11. Which species is larger, Na or Na+?

12. Which species is larger, Br or Br-?

49

Examples: Predicting Periodic Trends

13. Which species is larger, Sn2+ or Sn4+?

14. Which species is larger, Rb+ or Br-?

15. Arrange the following in order of increasing size:

Ca2+, S2-, Ar, K+, Cl-.

50
Chapter 8 Notes

Periodic Properties:
Ionization Energy,
Electron Affinity,
and
Metallic Character
51

Ionization Energy
• Ionization Energy (IE) — the amount of energy
needed to remove an electron from a mole of neutral
atoms in the gas phase:
M(g) → M+(g) + e-(g); ΔH° = IE (always > 0)
• Ionization energy is a positive energy value (an
endothermic process); energy must be provided in
order to remove an electron from an atom.
• The energy required to remove the first electron is
the first ionization energy (IE1).

52
MOV: Ionization Energies
Chapter 8 Notes

Trends in First Ionization Energy

• As we move down a group, atomic size increases, so
the outermost electrons become easier to remove,
since they are farther from the nucleus. Therefore,
ionization energy decreases as we move down a
group.
• As we move left-to-right across a period, Zeff
increases and atomic size decreases. As a result, the
outer electrons are held more tightly, and are harder
to remove. Therefore, ionization energy increases
as we move from left to right across a period.
• Atoms with low ionization energies (metals) tend to
form cations; those with high ionization energies
(nonmetals) tend to form anions.

53
MOV: Periodic Trends Ionization Energies

Ionization Energy vs. Atomic Number

54
Figure 8.14
Chapter 8 Notes

Trends in Ionization Energy

55
Figure 8.15

Exceptions to Trends in First Ionization Energy

• There are some variations in the general trends; the
variations result from the ionization of atoms which
have either one electron in a p subshell (B, Al), or
are one electron away from being half-filled (O, S).

56
Chapter 8 Notes

Higher Ionization Energies

• Of course, it is possible to form more than just 1+
cations:
M(g) → M+(g) + e-(g) first ionization energy (IE1)
M+(g) → M2+(g) + e-(g) second ionization energy (IE2)
M2+(g) → M3+(g) + e-(g) third ionization energy (IE3)

• More energy is required for each successive ionization

step (IE3 > IE2 > IE1) because it is harder to remove an
electron from a positively charged ion.
• Large jumps in ionization energy occur when we are
trying to remove electrons from filled shells.

57

Higher Ionization Energies

• Why is the third ionization
energy of Be so much higher
than the second and first?
Be 1s2 2s2
IE1

Be+ 1s2 2s1

IE2

Be2+ 1s2
IE3

Be3+ 1s1 58
Chapter 8 Notes

Higher Ionization Energies

59

Higher Ionization Energies

60
Chapter 8 Notes

Electron Affinity
• Electron Affinity (Eea) — the energy change
accompanying the addition of electrons to 1 mole of
atoms in the gas phase:
M(g) + e-(g) → M-(g); ΔH° = Eea (usually < 0)
• Electron affinity is usually a negative energy value
(an exothermic process); energy is usually released
when an electron is added to a neutral atom.
• The more negative the electron affinity, the greater
the tendency of the atom to accept an electron and
the more stable the resulting anion will be.
• In general, electron affinity decreases as we move
down a group, and increases from left to right,
but the trend is not as smooth as for ionization
energy and size.
61
MOV: Periodic Trends Electron Affinity

Electron Affinity

62
Figure 8.16
Chapter 8 Notes

Trends in Metallic Character

• Metals are good conductors of heat and electricity,
they are malleable and ductile, are often shiny, and
easily lose electrons in chemical reactions.
• Nonmetals are poor conductors of heat and
electricity, their physical states vary from solid to gas,
and they tend to gain electrons in chemical reactions.
• Moving from left to right across a period, ionization
energy increases and electron affinity becomes more
negative. Therefore, metallic character decreases as
we move from left to right across a period.
• As we move down a group, ionization energy
decreases, making electrons more likely to be lost.
Therefore, metallic character increases as we move
down a group.
63

Trends in Metallic Character

64
Figure 8.17
Chapter 8 Notes

Trends in Metallic Character

65
Figure 8.18

Summary of the Periodic Trends

66
Chapter 8 Notes

Examples: Predicting Periodic Trends

16. Which atom has the larger IE: Al or S?

17. Which atom has the larger IE: As or Sb?

18. Which atom has the larger IE: N or Si

19. Which atom has the larger IE: O or Cl?

20. Which atom has the largest IE: Na, Sr, Be, Rb?

67

Examples: Predicting Periodic Trends

21. Arrange the following in order of increasing IE:
F, S, Cl.

22. Which has the larger electron affinity, O or F?

23. Which element is more metallic: Sn or Te?

24. Which element is more metallic: Ge or In?

68