LO 4

 Learning Outcome: Through laboratory investigations develop operational definitions of chemical elements, differentiate between
metals/nonmetals and chemical and physical properties of unknown elements based on their position and atomic structures in the periodic table.

Key Concepts:

o 1. Structure of the periodic table.

o 2. Trends and Periodicity.

o 3. Atomic Radius.

o 4. Ionization Energy.

o 5. Electronegativity.

o 6. Electron Affinity.

o 7. Metal, nonmetal and metalloid.

Skills:
1. Draw and describe simple electronic configuration.

2. Describe the basis of the arrangement of elements

3. Use the periodic table to predict the properties of elements

4. Distinguish between metals and non-metals according to appearance

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 Biological Periodic Table

http://umbbd.ahc.umn.edu/
periodic/spiral.html

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Development of the Periodic Table
In 1864, John Newlands noted that when the elements were arranged in order of
atomic
number that every eighth element had
similar properties.
He referred to this as the law of octaves.
In 1869, Dmitri Mendeleev and
Lothar Meyer
independently proposed the idea of
periodicity .
Mendeleev grouped elements (66) according
to properties.
Mendeleev predicted properties for elements
not yet discovered, such as Ga
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Development of the Periodic Table
However, Mendeleev could not explain inconsistencies
such as argon coming before potassium in the periodic
table, despite having a higher atomic mass.
In 1913, Henry Moseley discovered the correlation
between the number of protons (atomic number ) and
frequency of X-rays generated.
Ordering the periodic table by atomic number instead
of atomic mass enabled scientists to make sense of
discrepancies.
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Dmitri Mendeleev (1869)

In 1869 Mendeleev and Lothar Meyer (Germany) published nearly identical

classification schemes for elements known to date. The periodic table is base on

the similarity of properties and re-activities exhibited by certain elements.

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Periodic Trends

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What is periodicity?
The term periodicity describes a repeating pattern in
properties of elements across periods of the periodic table.

The Russian chemist Dmitry

Mendeleev is credited with being the
creator of the first version of the
periodic table. He observed that when
the elements are arranged in order of
atomic mass, there are recurring
patterns in certain properties.

The modern periodic table can be used

to analyse trends in properties such as
atomic radius across periods and
down groups.

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Effective Nuclear Charge

• In a many-electron
atom, electrons are
both attracted to the
nucleus and repelled
by other electrons.
• The nuclear charge
that an electron
experiences depends
on both factors. Periodic
Properties
of the
Elements
© 2009, Prentice-Hall, Inc.
Effective Nuclear Charge

The effective nuclear

charge, Zeff, is found
this way:
Zeff = Z − S
where Z is the atomic
number and S is a
screening constant,
usually close to the
number of inner Periodic
Properties
electrons. of the
Elements
© 2009, Prentice-Hall, Inc.
Increase in proton number
The number of protons in the nucleus of the atoms
increases across period 3.

proton Element 11 Na 12 Mg 13 Al 14 Si 15 P 16 S 17 Cl 18 Ar
number

This increase in the number of protons increases the

nuclear charge of the atoms. The nucleus has stronger
attraction for the electrons, pulling them in closer and so
the atomic radius decreases across the period.
increased
nuclear charge
pulls electrons
closer

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Explaining atomic radius in period 3

Atomic Proton number increases

Proton across period 3, but
Element number radius
(nm) shielding remains
approximately constant.
Na 11 0.190
Mg 12 0.145 This causes an increase
Al 13 0.118 in effective nuclear
charge, leading to a
Si 14 0.111 greater attraction
P 15 0.098 between the nucleus and
the outermost electrons.
S 16 0.088
Cl 17 0.079 This pulls these electrons
closer to the nucleus and
Ar 18 0.071 results in a smaller radius.

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What is atomic radius?
The atomic radius of an element is difficult to precisely define
because of the uncertainty over the size of the electron cloud.
Several definitions are used.

One definition is half the shortest internuclear distance found

in the structure of the element.

For non-metallic elements, the

covalent radius is often used
as the atomic radius. This is half
the internuclear distance covalent
between two identical atoms in radius
a single covalent bond.

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More on atomic radius
For non-bonded adjacent atoms (e.g. in a covalent crystal of
a non-metallic element), the van der Waals radius is used as
a value for atomic radius. This is half the shortest internuclear
distance between two similar non-bonded atoms.

van der
Waals radius

For metallic elements, the metallic radius is often used as

the atomic radius. This is half the shortest internuclear
distance between two adjacent atoms in a metallic bond.

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Trends in atomic radius in period 3

Atomic The atomic radius of the elements

Element across period 3 decreases.
radius (nm)
Na 0.190 This might seem counter-
Mg 0.145 intuitive, because as the
numbers of sub-atomic particles
Al 0.118
increase, the radius might be
Si 0.111 expected to also increase.
P 0.098
However, more than 99% of the
S 0.088
atom is empty space – the
Cl 0.079 nucleus and electrons themselves
Ar 0.071 occupy a tiny volume of the atom.

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Sizes of Ions
• Ionic size depends
upon:
– The nuclear
charge.
– The number of
electrons.
– The orbitals in
which electrons
reside.

Periodic
Properties
of the
Elements
© 2009, Prentice-Hall, Inc.
Sizes of Ions
• Cations are
smaller than their
parent atoms.
– The outermost
electron is
removed and
repulsions
between electrons
are reduced.

Periodic
Properties
of the
Elements
© 2009, Prentice-Hall, Inc.
Sizes of Ions
• Anions are larger
than their parent
atoms.
– Electrons are
added and
repulsions
between electrons
are increased.

Periodic
Properties
of the
Elements
© 2009, Prentice-Hall, Inc.
 Sizes of Ions
• Ions increase in size
as you go down a
column.
– This is due to
increasing value of n.

Periodic
Properties
of the
Elements
© 2009, Prentice-Hall, Inc.
 Sizes of Ions

• In an isoelectronic series, ions have the same number of

electrons.
• Ionic size decreases with an increasing nuclear charge.

Periodic
Properties
of the
Elements
© 2009, Prentice-Hall, Inc.
Trends in Atomic Size

Periodic
Properties
of the
Elements
 Choose the
Larger Atom in Each Pair

• C or O
• Li or K
• C or Al
• Se or I?

Periodic
Properties
of the
Elements
Variation of atomic
(molar) volume
within each
period.

Periodic
Properties
of the
Elements
Atomic Radii

Periodic
Properties
of the
Elements
 Periodic
Properties
of the
Elements
An ion is formed when an atom, or group of atoms,
has a net positive or negative charge (why?).
If a neutral atom looses one or more electrons
it becomes a cation.

11 protons 11 protons
Na 11 electrons Na +
10 electrons

If a neutral atom gains one or more electrons

it becomes an anion.

17 protons Periodic
17 protons
Cl 17 electrons Cl- 18 electrons
Properties
of the
Elements
Cation is always smaller than atom from
which it is formed. Anion is always larger than
atom from which it is formed.
Periodic
Properties
of the
Elements
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What is ionization energy?
Ionization is a process in which atoms lose or gain electrons
and become ions.

The first ionization (I1) energy of an element is the energy

required to remove one electron from a gaseous atom.

M(g) → M+(g) + e-(g)

The second ionization (I2) energy involves the removal of a

second electron:
M+(g) → M2+(g) + e-(g)

Looking at trends in ionization energies can reveal useful

evidence for the arrangement of electrons in atoms and ions.

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Evidence for energy levels
Plotting the successive ionization energies of magnesium
clearly shows the existence of different energy levels, and
the number of electrons at each level.
6
Successive ionization
energies increase as more
ionization energy

5 electrons are removed.

4 Large jumps in the ionization

energy reveal where electrons
are being removed from the
3 next principal energy level,
such as between the 2nd and
2 3rd, and 10th and 11th ionization
th

th
th
2 nd
3 rd
4 th
5 th
6 th
7 th
8 th
9 th
1 st

energies for magnesium.

10

12
11

electron removed
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More evidence for energy levels
The first ionization energies of group 2 elements also show
evidence for the existence of different principal energy levels.
first ionization energy
900 Even though the nuclear
charge increases down the
800 group, the first ionization
energy decreases.
(kJ mol-1)

700
This means electrons are
600 being removed from
successively higher
500 energy levels, which lie
further from the nucleus
400
and are less attracted to
Be Mg Ca Sr Ba
the nucleus.
element
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What is first ionization energy?
Ionization is a process in which atoms lose or gain electrons
and become ions.

The first ionization energy of an element is the energy

required to remove one electron from a gaseous atom.

M(g) → M+(g) + e-

The first ionization energy is therefore a measure of the

strength of the attraction between the outermost electrons
and the nucleus.

The first ionization energies of the elements in periods 2

or 3 can give information about their electronic structure.

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General trend in first ionization energy
There is a general 1600
increase in the first 1400

ionization energy
ionization energies 1200

(kJ mol-1)
across period 3. 1000
800
Across period 3, the
600
proton number
increases but the 400
Na Mg Al Si P S Cl Ar
amount of shielding
element
does not change significantly.
The effective nuclear charge therefore increases.

The greater attraction between the nucleus and the

outermost electrons means that more energy is required to
remove an electron.

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 Trend in first ionization energy: exceptions
There are two exceptions to the general trend in first
ionization energy: both aluminium and sulfur have lower
ionization energies than might be expected.

energy (kJ mol-1) 1600

1400 lower
ionization

1200 ionization
1000 energies
800 than
expected
600
400
Na Mg Al Si P S Cl Ar
element

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First ionization energy of Al vs. Mg
The first ionization energy of aluminium is less than that
of magnesium, even though aluminium has a higher
nuclear charge.
The electron removed when aluminium is ionized is in a 3p
sub-level, which is higher in energy than the 3s electron
removed when magnesium is ionized. Removing an
electron from a higher energy orbital requires less energy.

magnesium aluminium

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First ionization energy of S vs. P
The first ionization energy of sulfur is less than that of
phosphorus, even though sulfur has a higher nuclear charge.

The highest energy electron in both phosphorus and sulfur is

in the 3p sub-level. However, in sulfur this electron is paired,
while in phosphorus each 3p orbital is singly occupied.
Mutual repulsion between paired electrons means less
energy is required to remove one of them.

phosphorus sulfur

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 Group Trends

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 Groups of Elements in the Periodic Table

Eight Groups (the representative elements):

I. Alkali metals: (H), Li, Na, K, Rb, Cs

II. Alkali earth metals: Be, Al, Ca, Sr, Ba, Ra
III. Boron family: B, Al, Ga, In, Tl
IV. Carbon family: C, Si, Ge, Sn, Pb
V. Nitrogen family: N, P, As, Sb, Bi
VI. Chalcogens O, S, Se, Te, Po
VII.Halogens F, Cl, Br, I, At
VIII. Noble gases: (He), Ne, Ar, Kr, Xe, Rn

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Na, Mg and Al: melting and boiling points
The melting and boiling points increase for the three metallic
elements from sodium to aluminium.

3000
This is because the
2500
temperature (K)

strength of the
2000 metallic bonds
boiling point
1500 increases. More
energy is needed to
1000 break the stronger
melting point
500 metallic bonds, so
0 melting and boiling
Na Mg Al points are higher.
element

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Na, Mg and Al: metallic bond strength
The increase in metallic bond strength from sodium to
aluminium is due to two factors:
1. Charge density. This is the ratio of an
ion’s charge to its size. Na+ ions are
large with a small charge, so have a
low charge density. Al3+ ions are smaller
with a larger charge, and so have a
higher charge density. They are
therefore more strongly attracted to the
delocalized electrons.
2. Number of free electrons. Sodium has one
free electron per metal ion, whereas
aluminium has three. This leads to more
attractions that must be broken in aluminium.

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Silicon
Silicon has a macromolecular
structure similar to that of
diamond.

Each silicon atom is

bonded to four
neighbouring silicon atoms
by strong covalent bonds.
These must be broken in
order for silicon to melt.
This requires a lot of
energy, so silicon's melting
and boiling points are high.

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Period 3 non-metals
The melting and boiling points of phosphorus, sulfur and
chlorine are much lower than those of silicon.
3500
This is because 3000

temperature (K)
they have a 2500
simple molecular 2000
structure with 1500
weak van der 1000
Waals forces 500
holding the 0
molecules together. Na Mg Al Si P S Cl Ar
element
Breaking these forces of attraction requires much less
energy than breaking covalent bonds.

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Do all metals corrode?
Metals behave differently when potassium
exposed to the environment.
sodium
A metal’s resistance to corrosion calcium
is related to its position in the magnesium
reactivity series. The more aluminium

increasing reactivity
reactive a metal, the less
zinc
resistant it is to corrosion.
iron
Gold is an unreactive metal lead
and does not corrode easily. copper
Items made from gold can silver
survive for thousands of years
gold
and have even been found in
good condition underwater. platinum

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What is rusting?
Rusting is the specific name given to the corrosion of iron.
It is a chemical reaction between iron, oxygen and water.
The chemical name for rust is hydrated iron (III) oxide.

Rusting is an example of an oxidation reaction.

Oxidation is the addition of oxygen to an element.

iron + oxygen + water  hydrated iron (III) oxide

The opposite process, where oxygen is removed from a

compound, is known as reduction.

Acid rain and salt can increase the rate of rusting.

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Typical properties of metals
What are the properties of metals?
 solid
 strong
 malleable (easily shaped)
 conduct heat and electricity
 dense
 shiny
 sonorous (make a ringing sound)
 ductile (can be pulled into wires)
 high melting and boiling points. Do all metals have
all these properties?

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Typical properties of non-metals
What are the properties of non-metals?
 usually liquids or gases
 non-rigid structure
 poor conductors of
heat and electricity
 low density
 dull, not shiny
 not ductile
 low melting and boiling points.

Do all non-metals have all these properties?

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Carbon
Carbon is a very common non-metal.
Carbon is the fourth most common element in the universe,
and nearly a fifth of the human body is made of carbon.
Carbon exists as a pure element in three forms:

Diamond, which Graphite, which Fullerenes,

is the hardest you will find in which are football-
substance known. your pencil. shaped molecules.

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Why doesn’t aluminium corrode?
Aluminium is a very reactive metal. However, it does
not corrode in the presence of oxygen. Why is this?
oxygen in the
atmosphere

coating of
oxygen atoms

aluminium
atoms

The outer aluminium atoms react with oxygen in the

atmosphere to form a thin layer of aluminium oxide on the
metal’s surface, which protects the metal from corrosion.

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 Alkali Metals
• Alkali metals are soft,
metallic solids.
• The name comes from the
Arabic word for ashes.

Periodic
Properties
of the
Elements
© 2009, Prentice-Hall, Inc.
 Alkali Metals
• They are found only in compounds in nature, not in their
elemental forms.
• They have low densities and melting points.
• They also have low ionization energies.

Periodic
Properties
of the
Elements
© 2009, Prentice-Hall, Inc.
 Alkali Metals

Their reactions with water are famously exothermic.

Periodic
Properties
of the
Elements
© 2009, Prentice-Hall, Inc.
 Alkali Metals
• Alkali metals (except Li) react with oxygen to
form peroxides.
• K, Rb, and Cs also form superoxides:
K + O2  KO2
• They produce bright colors when placed in a
flame.

Periodic
Properties
of the
Elements
© 2009, Prentice-Hall, Inc.
 Alkaline Earth Metals

• Alkaline earth metals have higher densities and melting points

than alkali metals.
• Their ionization energies are low, but not as low as those of
alkali metals.
Periodic
Properties
of the
Elements
© 2009, Prentice-Hall, Inc.
 Alkaline Earth Metals
• Beryllium does not react with
water and magnesium
reacts only with steam, but
the others react readily with
water.
• Reactivity tends to increase
as you go down the group.

Periodic
Properties
of the
Elements
© 2009, Prentice-Hall, Inc.
 Group 6A

• Oxygen, sulfur, and selenium are nonmetals.

• Tellurium is a metalloid.
• The radioactive polonium is a metal.
Periodic
Properties
of the
Elements
© 2009, Prentice-Hall, Inc.
Oxygen
• There are two allotropes of
oxygen:
– O2
– O3, ozone
• There can be three anions:
– O2−, oxide
– O22−, peroxide
– O21−, superoxide
• It tends to take electrons
from other elements
(oxidation). Periodic
Properties
of the
Elements
© 2009, Prentice-Hall, Inc.
 Sulfur

• Sulfur is a weaker
oxidizer than
oxygen.
• The most stable
allotrope is S8, a
ringed molecule.
Periodic
Properties
of the
Elements
© 2009, Prentice-Hall, Inc.
 Group VIIA: Halogens

• The halogens are prototypical nonmetals.

• The name comes from the Greek words halos
and gennao: “salt formers”.
Periodic
Properties
of the
Elements
© 2009, Prentice-Hall, Inc.
Group VIIA: Halogens
• They have large, negative
electron affinities.
– Therefore, they tend to
oxidize other elements
easily.
• They react directly with
metals to form metal
halides.
• Chlorine is added to water
supplies to serve as a
disinfectant Periodic
Properties
of the
Elements
© 2009, Prentice-Hall, Inc.
 Group VIIIA: Noble Gases

• The noble gases have astronomical ionization

energies.
• Their electron affinities are positive.
– Therefore, they are relatively unreactive.
Periodic
• They are found as monatomic gases. Properties
of the
Elements
© 2009, Prentice-Hall, Inc.
 Group VIIIA: Noble Gases

• Xe forms three
compounds:
– XeF2
– XeF4 (at right)
– XeF6
• Kr forms only one stable
compound:
– KrF2
• The unstable HArF was Periodic
Properties
of the
synthesized in 2000. Elements
© 2009, Prentice-Hall, Inc.
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 Atomic Radius
• Atomic radii actually Fig. 8.17 Atomic Radii for Main
decrease across a Group Elements
row in the periodic
table. Due to an
increase in the
effective nuclear
charge.
• Within each group
(vertical column),
the atomic radius
tends to increase
with the period 8–83

number.
John A. Schreifels Chapter 8-83
Chemistry 211
 Atomic Radius 2
• If positively charged the radius decreases
while if the charge is negatively the radius
increases (relative to the atom).
• When substances have the same number of
electrons (isoelectronic), the radius will
depend upon which has the largest number of
protons.
E.g. Predict which of the following substances
has the largest radius: P3, S2, Cl, Ar, K+,
Ca2+. 8–84

John A. Schreifels Chapter 8-84

Chemistry 211
 IONIZATION ENERGY
• Ionization energy, Ei: minimum energy required to remove an
electron from the ground state of atom (molecule) in the gas phase.
M(g) + h  M+ + e.
• Ei related to electron configuration. Higher energies = stable ground
states.
• Sign of the ionization energy is always positive, i.e. it requires energy
for ionization to occur.
• The ionization energy is inversely proportional to the radius and
directly related to Zeff.
• Exceptions to trend:
– B, Al, Ga, etc.: their ionization energies are slightly less than the
ionization energy of the element preceding them in their period.
• Before ionization ns2np1.
• After ionization is ns2. Higher energy  smaller radius.
– Group 6A elements.
• Before ionization ns2np4.
• After ionization ns2np3 where each p electron in different orbital (Hund’s rule).
• Electron-electron repulsion by two electrons in same orbital 8–85
increases the energy (lowers EI).

John A. Schreifels Chapter 8-85

Chemistry 211
 Ionization Energy: Periodic table
Fig. 8.18 Ionization Energy vs atomic #

8–86

John A. Schreifels Chapter 8-86

Chemistry 211
 HIGHER IONIZATION ENERGIES
• The energies for the subsequent loss of more electrons are
increasingly higher. For the second ionization reaction written as
• M+(g) + h  M2+ + e Ei2.
• Large increases in the ionization energies vary in a zig-zag way
across the periodic table.
• States with higher ionization energies have: 1s22s22p6 (stable).

8–87

John A. Schreifels Chapter 8-87

Chemistry 211
 ELECTRON AFFINITY
• Electron Affinity, Eea, is the
energy change that occurs
when an isolated atom in the
gas phase gains an electron.
E.g. Cl + e  Cl Eea = 348.6
kJ/mol
• Energy is often released during
the process.
• Magnitude of released energy
indicates the tendency of the
atom to gain an electron.
– From the data in the table the
halogens clearly have a strong
tendency to become negatively
charged 8–88
– Inert gases and group I & II
elements have a very small Eea.
John A. Schreifels Chapter 8-88
Chemistry 211