Chapter 7

Periodic Properties of
the Elements
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 Factors Affecting Atomic Orbital Energies
The Effect of Nuclear Charge (Zeffective) E (Zeff x e-)
r
Zeff = Z S (S = charge of intervening core electrons)
Higher nuclear charge lowers orbital energy (stabilizes the system)
by increasing nucleus-electron attractions. Orbital shape
penetration of s-orbitals

The Effect of Electron Repulsions (Shielding)

Additional electron in the same orbital

An additional electron raises the orbital energy through

electron-electron repulsions.

Additional electrons in inner orbitals

Inner electrons shield outer electrons more effectively than do

electrons in the same sublevel.
Slaters Rules: S3p = [0.35(# valence
electrons 1) + 0.85(#
electrons in next lower
electron energy level) + #
of remaining electrons

For Cl:
1s22s22p63s23p5

S = [(0.35 * 6) +
(0.85 * 8) + 2)]
= 10.9

Zeff = 17 10.9 = 6.1 for

a 3p electron

E (Zeff x e-)
r
 Periodic Trends
Atomic Radii:
decrease going from left to right
across a period;
increase going down a group.
 Zeff = (3 2)=+1 Zeff = (5 2) =Z+3= (9-2)=+7)
eff
Zeff=(4-2) =+2

Atomic radii of the main-

group and transition
elements.

Radius is

Zeff = Z (# core electrons)

Periodicity of atomic radius.
Defining metallic and covalent
(bonding) radii.

Nonbonding
radius
Bond length and covalent (bonding) radius.
Internuclear distance Covalent Internuclear distance Covalent
(bond length) radius (bond length) radius

72 pm 114 pm

Internuclear distance Covalent Internuclear distance Covalent

(bond length) radius (bond length) radius

100 pm 133 pm
Main-group ions and the noble gas configurations Octet Rule.
Some common monatomic ions of the elements.

Can you see any patterns?

 Guidelines for Forming Monatomic Ions
Electrons with the highest n value are removed first.
For main-group s-block elements, remove all electrons
with the highest ns value: Ca Ca2+ + 2 e-
For main-group p-block elements, remove highest np
electrons before removing ns electrons: N (valence
configuration = 2s2 2p3) loses 2p electrons before the 2s
electrons. NO2- oxidation state for N is 3+, NO3-, oxidation state for N is 5+
For nonmetal anions, add electrons to the p orbitals with the
highest n value.
For transition (d-block) elements, remove the ns electrons
before the (n-1)d electrons
 Electron Configurations of Ions
As metals lose electrons to form cations and
establish a noble gas configuration, the electrons
are lost from the valence shell first.
For example, magnesium generally loses two
electrons from its 3s subshell to look like neon.
Mg Mg2+ + 2 e-
[Ne]3s2 [Ne]
Thallium (Tl) can lose one electron from its 6p
subshell or one electron from its 6p and two
electrons from its 6s subshells to form
Tl Tl+
+ 1 e- [Xe]4f145d106s26p1 [Xe]4f145d106s2
Tl Tl3+ + 3 e- [Xe]4f145d106s26p1 [Xe]4f145d10
 Electron Configurations of Ions

As nonmetals can gain electrons to form anions and

establish a noble gas configuration, or lose
electrons in covalent bond formation.

For example, phosphorus generally can gain

three electrons in its 3p subshell to look like Ar.
P + 3 e- P3-
[Ne]3s23p3 [Ne]3s23p3 or [Ar]

4 P + 5 O2 2 P2O5
[Ne]3s23p3 [Ne]
 Electron Configurations of Ions
Transition metals also lose electrons from the
valence shell first, which is not the last subshell to fill
according to the aufbau sequence.

For example, zinc generally loses two electrons

from its 4s subshell to adopt a pseudo-noble
gas configuration.

Zn Zn2+ + 2 e-
[Ar]4s23d10 [Ar]3d10
Noble gas configuration + filled d subshell = pseudocore
Ionic vs. atomic radii.

All isoelectronic with

Neon
 SAMPLE PROBLEM Writing Electron Configurations of Main-Group Ions

PROBLEM: Using condensed electron configurations, write reactions for the

formation of the common ions of the following elements:
(a) Iodine (Z = 53) (b) Potassium (Z = 19) (c) Indium (Z = 49)

PLAN: Ions of elements in Groups 1A(1), 2A(2), 6A(16), and 7A(17) are usually
isoelectronic with the nearest noble gas.
Metals in Groups 3A(13) to 5A(15) can lose their np or ns and np electrons.

SOLUTION:
(a) Iodine (Z = 53) is in Group 7A(17) and will gain one electron to be isoelectronic with Xe:
I ([Kr]5s24d105p5) + e- I- ([Kr]5s24d105p6)

(b) Potassium (Z = 19) is in Group 1A(1) and will lose one electron to be isoelectronic with Ar:
K ([Ar]4s1) K+ ([Ar]) + e-

(c) Indium (Z = 49) is in Group 3A(13) and can lose either one electron or three electrons: In
([Kr]5s24d105p1) In+ ([Kr]5s24d10) + e+
In ([Kr]5s24d105p1) In3+([Kr] 4d10) + 3e-
SAMPLE PROBLEM 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: Compare positions in the periodic table, formation of positive and

negative ions and changes in size due to gain or loss of electrons.

SOLUTION:

(a) Sr2+ > Ca2+ > Mg2+ These are members of the same Group (2A/2) and
therefore decrease in size going up the group.

(b) S2- > Cl - > K+ The ions are isoelectronic; S2- has the smallest Zeff and therefore
is the largest while K+ is a cation with a large Zeff and is the
smallest.
(c) Au+ > Au3+ The higher the + charge, the smaller the ion.
 The nonmetallic element, sulfur, belongs to
group VIA (16). What is the most likely
sulfur ion formed when sulfur combines
with a metal metal ion?
% 1. S+
% 2. S2+
% 3. S-
% 4. S2-
 Magnetic Properties

Although an electron behaves like a tiny magnet, two

electrons that are opposite in spin cancel each other.
Only atoms with unpaired electrons exhibit magnetic
susceptibility.
A paramagnetic substance is one that is
weakly attracted by a magnetic field, usually
the result of unpaired electrons.
A diamagnetic substance is not attracted by a
magnetic field generally because it has only
paired electrons.
Apparatus for measuring the magnetic behavior of a sample.
SAMPLE PROBLEM Writing Electron Configurations and Predicting
Magnetic Behavior of Transition Metal Ions

PROBLEM: Use condensed electron configurations to write the reaction for the
formation of each transition metal ion, and predict whether the ion is
paramagnetic.
(a) Mn2+(Z = 25) (b) Fe3+(Z = 26) (c) Hg2+(Z = 80)

PLAN: Write the electron configuration and remove electrons starting with ns to
match the charge on the ion. If the remaining configuration has unpaired
electrons, it is paramagnetic.
SOLUTION:
(a) Mn2+(Z = 25) Mn([Ar]4s23d5) Mn2+ ([Ar] 3d5) + 2e- paramagnetic

(b) Fe3+(Z = 26) Fe([Ar]4s23d6) Fe3+ ([Ar] 3d5) + 3e- paramagnetic

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

diamagnetic
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 Ionization Energy

The quantity of energy

required to remove an electron
from the gaseous atom or ion.
Na (g) Na+ (g) + e-
Ionization energies are endothermic

[Ne]3s1 [Ne] + e-
Ionization is an oxidation
Periodicity of first ionization energy (IE1).
 First ionization energies of the main-group elements.

Energy = Force x distance

kZeffe- x r = kZeffe- = I.E.

r2 r
The first three ionization energies of beryllium (in
MJ/mol).

For more data on sequential

ionization energies of the elements,
go to http://www.webelements.com or
click on the button below.

This is an oxidation

Be (g) Be+ (g) + e- E = I.E. 1

Be+ (g) Be2+ (g)+ e- E = I.E. 2
Be (g) Be2+ (g) + 2 e- E = I.E. 1 + I.E. 2
E = 2.66 MJ/mol
SAMPLE PROBLEM Ranking Elements by First Ionization Energy

PROBLEM: Using the periodic table only, rank the elements in each of the following
sets in order of decreasing IE1:
(a) Kr, He, Ar (b) Sb, Te, Sn (c) K, Ca, Rb (d) I, Xe, Cs

PLAN: IE decreases as you proceed down in a group; IE increases as you go

across a period.

SOLUTION:
(a) He > Ar > Kr Group 8A(18) - IE decreases down a group.

(b) Te > Sb > Sn Period 5 elements - IE increases across a period.

(c) Ca > K > Rb Ca is to the right of K; Rb is below K.

(d) Xe > I > Cs I is to the left of Xe; Cs is further to the left and down
one period.
SAMPLE PROBLEM Identifying an Element from Successive
Ionization Energies

PROBLEM: Name the Period 3 element with the following ionization energies (in
kJ/mol) and write its electron configuration:
IE1 IE2 IE3 IE4 IE5 IE6
1012 1903 2910 4956 6278 22,230

PLAN: Look for a large increase in energy which indicates that all of the valence
electrons have been removed.

SOLUTION:
The largest increase occurs after IE5, that is, after the 5th valence electron
has been removed. Five electrons would mean that the valence
configuration is 3s23p3 and the element must be phosphorous, P (Z = 15).
The complete electron configuration is 1s22s22p63s23p3.
The atomic radius of Phosphorus is 110 pm and its first
ionization energy is 1012 kJ/mole. Predict the
properties of an element with a lower atomic number
in the same period using your knowledge of atomic
trends in radius and ionization energies.
Element Radius, pm Ionization Energy, kJ/mole

8%
1. A 95 1100
4%
2. B 115 1256
84%
3. C 113 986
4%
4. D 85 1520
 Electron Affinity

The energy change associated

with the addition of an electron to a
gaseous atom.
X(g) + e X(g)

Most electron affinities are exothermic

Electronic affinity is a reduction

 Periodic Properties

Electron Affinity
The electron affinity is the energy
change for the process of adding an
electron to a neutral atom in the gaseous
state to form a negative ion.

For a chlorine atom, the first electron affinity

is illustrated by:
Cl ([Ne]2s22p5) + e- Cl- ([Ne]2s22p6)
Electron Affinity = -349 kJ/mol
Electron affinities of the main-group elements.
 Trends in three atomic properties.
Increases means becomes larger
(requires more energy for I. E.)

FIRST

Zeff important contributor to row

trends
E = (Zeff x e)/r
Atomic size to group trends

Increases means becomes more negative or more energy is released

for electron affinity!
 Summary

Energy required to remove an electron from an atom:

E (Zeff x e-) ,where Zeff is the net positive charge felt by the electron, e- is
the r charge of the electron, and r is the distance between the
nucleus and outermost electrons.

Zeff = Z S, where Z is the atomic number and S is the # of intervening core

electrons. The core electrons shield with nearly 100% efficiency, while
electrons in the same sublevel shield less efficiently. The influence of Zeff is
most important in predicting atomic radius and ionization energy trends
going from left to right across a period. The influence of r is most important
in explaining these trends within a group.
Electron affinities are highest in nonmetals and can be used to predict
metallic character. Electron affinities become more positive going down a
group, and become more negative going from left to right within a period.
 Trends in metallic behavior.

Metallic behavior is associated with low

ionization energies and more + electron
affinities (less energy released when a e- is
added to an outer orbital)
 A general comparison of metals and nonmetals.
d & s-block

p-block
elements

s-block
elements
f-block
elements
E = Zeff e-
r
Zeff = Z core electrons
Chemistry of the Group 1A Elements:
Alkali Metals
Reaction with Halogens
2M(s) + X2 2MX(s) M = Li, Na, K, Rb, or Cs
X = F, Cl, Br, or I
Reaction with Oxygen
4Li(s) + O2(g) 2Li2O(s) oxide
2Na(s) + O2(g) Na2O2(s) peroxide
Reaction with Water
2M(s) + 2H2O(l) 2M1+(aq) + 2OH1-(aq) + H2(g)
M = Li, Na, K, Rb, or Cs
Some Properties & Reactions of Pure Substances

2 Na (s)+ Cl2 (g) 2 NaCl (s)

 Chemistry of the Group 2A Elements:
Alkaline Earth Metals

Metallic Relatively soft (harder than 1a)

Bright, silvery Not as reactive as 1a
Occur only in salts
Chemistry of the Group 2A Elements:
Alkaline Earth Metals
Reaction with Halogens
M + X2 MX2 M = Be, Mg, Ca, Sr, or Ba
X = F, Cl, Br, or I
Reaction with Oxygen
2M + O2 2MO M = Be, Mg, Ca, Sr, or Ba

Reaction with Water

M(s) + 2H2O(l) M2+(aq) + 2OH1-(aq) + H2(g)

M = Mg, Ca, Sr, or Ba

 The trend in acid-base
behavior of element
oxides.

Most main-group
metals transfer electrons
to oxygen they
form ionic bonds with
oxygen which dissociate
In water
NaOH Na+ + OH-
So the metal O bond
More easily broken (i.e.,
O-H is stronger)
For nonmetal oxides, bonding to O is covalent
and O-H bond is usually the weaker so
these compounds donate H in reactions.
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 Chapter 8
Basic Concepts of
Chemical Bonding
 Bonding

A chemical bond forms when the potential

energy of the bonded atoms is lower than the
potential energy of the separate atoms.
To calculate, you need to consider the following
interactions:
nucleus-to-nucleus repulsions
electron-to-electron repulsions
nucleus-to-electron attractions

46
 Types of Chemical Bonding

1. Metal with nonmetal:

electron transfer and ionic bonding
2. Nonmetal with nonmetal:
electron sharing and covalent bonding
3. Metal with metal:
electron pooling and metallic bonding
The three models of chemical bonding.
 Ionic Bonds

Formed from electrostatic attractions of

closely packed, oppositely charged ions.

Formed when an atom that easily loses

electrons reacts with one that has a high
electron affinity.
Covalent bond formation in H2.

The distance where the system energy

is a minimum = bond length
Distribution of electron density of H2.
Electron density distributions in H2, F2, and HF.
 Electronegativity
The ability of an atom in a molecule to
attract shared electrons to itself.
Calculated using difference between
experimental bond energy and
expected bond energy assuming equal
sharing of bonding pair
= (H X)actual (H X)expected

Expected H-X bond energy = H-H b.e. + X-X b.e.

2
 Electronegativity
Electronegativity is a measure of the ability of
an atom in a molecule to draw bonding
electrons to itself.
In general, electronegativity increases from the
lower-left corner to the upper-right corner of
the periodic table (same as Zeff).
The current electronegativity scale, developed
by Linus Pauling, assigns a value of 4.0 to
fluorine and a value of 0.7 to cesium.
The Pauling electronegativity (EN) scale.
Boundary ranges for classifying ionic character of
chemical bonds.
3.0

EN

2.0

0.0
 Polarity of Bonds

A molecule, such as HF, that has a center

of positive charge and a center of negative
charge is said to be polar, or to have a dipole
moment.
The effect of an electric field on hydrogen fluoride molecules.
(a) When no electric field is present, the molecules are randomly oriented.
(b) When the field is turned on, the molecules tend to line up with their
negative ends toward the positive pole and their
positive ends toward the negative pole.
 Bond Dipole Moments
Dipole moment, m, is a measure of bond polarity.
A dipole is a material with a + and end.
It is directly proportional to the size of the partial charges and
directly proportional to the distance between them .
m = qr
not Coulombs law
measured in debyes, D
Generally, the more electrons two atoms share and the
larger the atoms are, the larger the dipole moment.
The percent ionic character is the ratio of a bonds
measured dipole moment to what it would be if it were
completely ionic.

59
The relationship between the ionic character of a covalent
bond and the electronegativity difference of the bonded
atoms.

ionic

covalent
 Dipole Moments

61
 SAMPLE PROBLEM Determining Bond Polarity from EN Values

PROBLEM: (a) Use a polar arrow to indicate the polarity of each bond: N-
H, F-N, I-Cl.
(b) Rank the following bonds in order of increasing polarity: H-
N, H-O, H-C.
PLAN: (a) Use Figure 4.3 (textbook) to find EN values; the arrow
should point toward the negative end.
(b) Polarity increases across a period.

SOLUTION: (a) The EN of N = 3.0, H = 2.1; F = 4.0; I = 2.5, Cl = 3.0

N-H F-N I - Cl
0.9 1.0 0.5
(b) The order of increasing EN is C < N < O; all have an EN
larger than that of H.
H-C < H-N < H-O
 3A 4A 5A 6A 7A
1A 2A

Properties of the Period 3 chlorides.

 Which compound has the most polar
bond?
A. HF
55%
B. HCl
C. HBr
D. HI
27%

15%

3%

r
HF

HI
HC

HB
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Lattice Energy is defined as the
amount of energy released during the
formation of 1 mole of a crystalline
ionic solid from its respective gas
phase cations and anions.

Na+ (g) + Cl- (g) NaCl (s) lattice

energies are exothermic
using this definition
 Periodic Trends in Lattice Energy
Coulombs Law
K x (charge A X charge B)
K = constant
electrostatic force =
distance2 Let distance = distance
between bonding nuclei
energy = force X distance therefore
K x(charge A X charge B)
electrostatic energy =
distance

K (cation charge X anion charge)

Lattice energy =
cation radius + anion radius
-
Trends in lattice energy.

-
electrostatic energy =
K x( charge A X charge B)
-
distance

-
Energetics of ionic bonding.
Lattice Energy: Na+(g) + Cl-(g) NaCl(s)

(- Lattice
Energy)
 Calculation of NaCl lattice energy
Na+ (g) + Cl- (g) NaCl (s) - Hlattice

1. Na + (g) + e Na (g) -495 kJ ( - I.E.)

2. Na (g) Na (s) -109 kJ (-heat of sublimation)

3. Na (s) + Cl2 (g) NaCl (s) -411 kJ (heat of formation )

4. Cl (g) Cl2 (g) -119.5 kJ ( -bond energy)

5. Cl- (g) Cl (g) + e + 349 kJ (-electron affinity)

Na+ (g) + Cl- (g) NaCl (s) -786 kJ (- lattice energy)

Melting and Boiling Points of Some Ionic Compounds

Compound mp (0C) bp (0C)

CsBr 636 1300

NaI 661 1304
MgCl2 714 1412
KBr 734 1435
CaCl2 782 >1600
NaCl 801 1413
LiF 845 1676
KF 858 1505
MgO 2852 3600
electrostatic energy =
K x( charge A X charge B)
Charge on ions: Mg2+ , O2- distance
 Lewis Structure

Shows how valence electrons are arranged

among atoms in a molecule.
Reflects central idea that stability of a
compound relates to noble gas electron
configuration ns2 np6 or octet rule.
G.N. Lewis and Linus Pauling developed
these concepts about 80 years ago.
 Lewis Electron-Dot Symbols

For main group elements -

The representative (A) group number gives the number of

valence electrons.
Place one dot per valence electron on each of the
four sides of the element symbol.
Pair the dots (electrons) until all of the valence
electrons are used.
Example: Nitrogen, N, is in Group 5A and has 5 valence
electrons (2s22p3).
. . .
. N: . N.
:

: N. .N .
. .

:
.
Lewis electron-dot symbols for elements in
Periods 2 and 3.
 Three ways to represent the formation of Li+ and F-
through electron transfer.
Electron configurations
Li 1s22s1 + F 1s22s22p5 Li+ 1s2 + F- 1s22s22p6

Orbital diagrams
Li+
Li
1s 2s 2p
1s 2s 2p

+ F + F-

1s 2s 2p 1s 2s 2p

Lewis electron-dot symbols

.

:
Li . + :F : Li+ + : F :-

:
:
 SAMPLE PROBLEM Depicting Ion Formation
PROBLEM: Use partial orbital diagrams and Lewis symbols to depict the
formation of K+ and O2- ions from the atoms, and determine
the formula of the compound.
PLAN: Draw orbital diagrams for the atoms and then move electrons
to make filled outer levels. It can be seen that 2 potassium
atoms are needed for each oxygen.
SOLUTION: O2- is isoelectronic with Ne

O2-
K
2s 2p
4s 4p O

2s 2p 2 K+ Isoelectronic with Ne
K
K

.
.

:
4s 4p + :O: 2K+ + : O :2-

.
K

:
.
Isoelectronic with Ar
Comparison of Ionic and Covalent Compounds

Ionic Compounds
Bonding involves transfer of one or more electrons from one bonding
atom (cation) to the other (anion)
Formula unit is the empirical formula. Solid structures consist of
repeating cations and anions. Lattice energy is the amount energy
required to convert 1 mole of formula units to gas phase ions.

Covalent Compounds
Bonding involves sharing of one, two, or three pairs of electrons
by bonding atoms
Exist as discreet molecules which consist of one or more empirical
formulas. Solid structures consist of repeating molecules.

Standard heats of reaction, H0, may be determined from bond energies

of reactants and products