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Chapter 8.

Periodic Properties of the Element

Modified by Dr. Cheng-Yu Lai

Energy Diagram for Hydrogen Atom


The energy of a particular orbital is determined by its value
of n. All orbitals with the same value of n have the same
energy and are said to be degenerate. Hydrogen single
electron occupy the lowest energy state, the ground state.
If energy is put into the system, the electron can be
transferred to higher energy orbital called excited state.
For a one-electron
hydrogen atom,
orbitals on the same
energy level have the
same energy.
That is, they are
degenerate.

H : 1s1

Orbital Energy
Levels for the
Hydrogen Atom

Electron Energy in Hydrogen-like Charge Atoms


2

Z
18
Eelectron 2.178 x 10 J 2
n

Z = nuclear charge (atomic number)


n = energy level or principal quantum number (n) = 1, 2, 3, 4,

***Equation works only for atoms or ions with 1 electron


(H, He+, Li2+, etc).
Rydbergs constant (RH) = 2.178 x 10-18 J
Johannes Rydberg
(1854-1919)

Energy Orbitals for Polyelectronic Atoms


As the number of
electrons increases,
though, so does the
repulsion between
them.
Therefore, in manyelectron atoms, orbitals
on the same energy
level are no longer
degenerate.
For a given principal quantum level the
orbitals vary in energy as follows:
Ens< Enp < End < Enf

Aufbau Principle -- Bottom Up Rule

Start by drawing a diagram,


putting each energy shell on
a row and listing the sublevels
(s, p, d, f) for that shell in
order of energy (from left to
right).
Next, draw arrows through
the diagonals, looping back
to the next diagonal
each time.

1s

2s

2p

3s

3p

3d

4s

4p

4d

4f

5s

5p

5d

5f

6s

6p

6d

7s
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Basic Principle:
electrons occupy
lowest energy
levels available

Rules for Filling Orbitals


Bottom-up
(Aufbaus principle)

Fill orbitals singly before doubling up


(Hunds Rule)
Paired electrons have opposite spin
(Pauli exclusion principle)

Rules for Electron Configurations


of Multielectron Atoms
Electron Configuration: A description of which
orbitals are occupied by electrons
Degenerate Orbitals: Orbitals that have the
same energy level. For example, the three p
orbitals in a given subshell

Ground-State Electron Configuration: The


lowest-energy configuration
Aufbau Principle (building up): A guide for
determining the filling order of orbitals
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Chapter 5/7

Ruls for Electron Configurations of Multielectron


Atoms
Rules of the aufbau principle:
1. Lower-energy orbitals fill before higher-energy orbitals.
2. An orbital can only hold two electrons, which must
have opposite spins (Pauli exclusion principle).
3. If two or more degenerate orbitals are available, follow
Hunds rule.
Hunds Rule: If two or more orbitals with the same energy
are available, one electron goes into each until all are halffull. The electrons in the half-filled orbitals all have the
same value of their spin quantum number.
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Chapter 5/8

2 ways to write electron configurations


spdf NOTATION
for H, atomic number = 1
no. of
1
electrons

spdf Notation

1s

sublevel
value of energy level

Orbital Box Notation

ORBITAL BOX NOTATION


for He, atomic number = 2

1s

1s

Arrows show
electron spin
(+ or -)

Electron Configurations of
Multielectron Atoms
Electron
Configuration

H:

1s1

1 electron
s orbital (l = 0)
n=1

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Chapter 5/10

Electron Configurations of
Multielectron Atoms
Electron
Configuration

H:

1s1

He:

1s2

2 electrons
s orbital (l = 0)
n=1

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Chapter 5/11

Electron Configurations of
Multielectron Atoms
Electron
Configuration

H:
He:
Li:

1s1
1s2
Lowest energy to highest energy
1s2 2s1
1 electron
s orbital (l = 0)
n=2

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Chapter 5/12

Electron Configurations of
Multielectron Atoms
Electron
Configuration

H:

1s1

He:

1s2

Li:

1s2 2s1

N:

1s2 2s2 2p3

3 electrons
p orbital (l = 1)
n=2

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Chapter 5/13

Orbital Diagrams
As protons are added one by one to the nucleus to
build up the elements, electrons are similarly added
to these hydrogen-like orbitals.
Each box represents
one orbital.
Half-arrows represent
the electrons.
The direction of the
arrow represents the
spin of the electron.

H : 1s1, He : 1s2, Li : 1s2 2s1, Be : 1s2 2s2 B : 1s2 2s2 2p1,


C : 1s2 2s2 2p2.

Electron Configurations of Multielectron Atoms

Hunds Rule
For degenerate orbitals, the
lowest energy is attained when
the number of electrons with the
same spin is maximized.

N : 1s2 2s2 2p3, O : 1s2 2s2 2p4,


F : 1s2 2s2 2p5, Ne : 1s2 2s2 2p6,
Na : 1s2 2s2 2p63s1 OR [Ne] 3s1

Electron Configurations of
Multielectron Atoms
Electron
Configuration

H:

Orbital-Filling
Diagram

1s1
1s

He:

1s2

Li:

1s2 2s1

N:

1s2 2s2 2p3

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Chapter 5/16

Electron Configurations of
Multielectron Atoms
Electron
Configuration

H:

Orbital-Filling
Diagram

1s1
1s

He:

1s2

1s

Li:

1s2 2s1

N:

1s2 2s2 2p3

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Chapter 5/17

Electron Configurations of
Multielectron Atoms
Electron
Configuration

H:

Orbital-Filling
Diagram

1s1
1s

He:

1s2

1s

Li:

1s2 2s1

N:

1s2 2s2 2p3

1s 2s

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Chapter 5/18

Electron Configurations of
Multielectron Atoms
Electron
Configuration

H:

Orbital-Filling
Diagram

1s1
1s

He:

1s2

1s

Li:

1s2 2s1

N:

1s2 2s2 2p3

1s 2s

1s 2s

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2p
Chapter 5/19

Element

Lithium

Configuration
notation

Orbital notation

1s22s1

[He]2s1
____
1s

Beryllium

____

____
2p

____
[He]2s2

____
2s

____

____
2p

____

1s22s2p1

[He]2s2p1
____
1s

Carbon

1s22s2p2

Nitrogen

1s22s2p3

Oxygen

1s22s2p4

Fluorine

1s22s2p5

____
2s

____

____
2p

____

[He]2s2p2
____
1s

____
2s

____

____
2p

____
[He]2s2p3

____
1s

____
2s

____

____
2p

____
[He]2s2p4

____
1s

____
2s

____

____
2p

____
[He]2s2p5

____
1s
Neon

____
2s

1s22s2

____
1s
Boron

Noble gas
notation

____
2s

____

____
2p

____

1s22s2p6

[He]2s2p6
____
1s

____
2s

____

____
2p

____

Phosphorus

Symbol: P
Atomic Number: 15

Full Configuration: 1s22s22p63s23p3

Valence Configuration: 3s23p3


Shorthand Configuration: [Ne]3s23p3

Box Notation

1s

2s

2p

3s

3p

Electron Configurations of Multielectron Atoms


Na:

Electron
Configuration

Shorthand
Configuration

1s2 2s2 2p6 3s1

[Ne] 3s1

Ne configuration
P:

1s2 2s2 2p6 3s2 3p3

[Ne] 3s2 3p3

Ne configuration
K:

[Ar] 4s1

1s2 2s2 2p6 3s2 3p6 4s1


Ar configuration

Sc:

1s2 2s2 2p6 3s2 3p6 4s2 3d1


Ar configuration

[Ar] 4s2 3d1

Valence Shell: Outermost shell


electrons .

Example 8.1 Electron Configurations


Write electron configurations for each element.
a. Mg
b. P

c. Br

d. Al

Solution
a. Mg
Magnesium has 12 electrons. Distribute 2 of these into the 1 s orbital, 2 into the 2s orbital, 6 into the 2p orbitals,
and 2 into the 3s orbital.
Mg 1s2 2s2 2p6 3s2 or [Ne] 3s2
b. P
Phosphorus has 15 electrons. Distribute 2 of these into the 1s orbital, 2 into the 2s orbital, 6 into the 2p orbitals,
2 into the 3s orbital, and 3 into the 3p orbitals.
P 1s2 2s2 2p6 3s2 3p3 or [Ne] 3s2 3p3
c. Br
Bromine has 35 electrons. Distribute 2 of these into the 1s orbital, 2 into the 2s orbital, 6 into the 2p orbitals, 2
into the 3s orbital, 6 into the 3p orbitals, 2 into the 4s orbital, 10 into the 3d orbitals, and 5 into the 4p orbitals.
Br 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p5 or [Ar] 4s2 3d10 4p5
d. Al
Aluminum has 13 electrons. Distribute 2 of these into the 1s orbital, 2 into the 2s orbital, 6 into the 2p orbitals, 2
into the 3s orbital, and 1 into the 3p orbital.
Al 1s2 2s2 2p6 3s2 3p1 or [Ne] 3s2 3p1
Chemistry: A Molecular Approach, 3rd Edition
Nivaldo J. Tro

2014 Pearson Education, Inc.

Example 8.2 Writing Orbital Diagrams


Write the orbital diagram for sulfur and determine the number of unpaired electrons.

Solution
Since sulfurs atomic number is 16, it has 16 electrons and the electron configuration 1s2 2s2 2p6 3s2 3p4. Draw a
box for each orbital, putting the lowest energy orbital (1s) on the far left and proceeding to orbitals of higher
energy to the right.

Distribute the 16 electrons into the boxes representing the orbitals, allowing a maximum of 2 electrons per orbital
and remembering Hunds rule. You can see from the diagram that sulfur has two unpaired electrons.

Two unpaired electrons

Chemistry: A Molecular Approach, 3rd Edition


Nivaldo J. Tro

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Valence Electrons
The electrons in the outermost principle quantum
level of an atom.
Atom
Valence Electrons
Ca

Br
7
Valence electron is the most important electrons
to us because they are involved in bonding.
Elements with the same valence electron
configuration show similar chemical behavior.
Inner electrons are called core electrons.

Electron Configurations and


the Periodic Table
Valence Shell: Outermost shell electrons .

Li: 2s1
Na: 3s1
Cl: 3s2 3p5
Br: 4s2 4p5

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Chapter 5/26

Electron Configurations and


the Periodic Table

Example 8.3 Valence Electrons and Core Electrons


Write the electron configuration for Ge. Identify the valence electrons and the core electrons.

Solution
Write the electron configuration for Ge by determining the total number of electrons from germaniums atomic
number (32) and then distributing them into the appropriate orbitals.
Ge 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p2

sodium

1s22s22p63s1

iron

1s22s22p63s23p64s23d6

bromine 1s22s22p63s23p64s23d104p5
barium

Chemistry: A Molecular Approach, 3rd Edition


Nivaldo J. Tro

1s22s22p63s23p64s23d104p65s24d105p66s2

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Irregular Electron Configurations


There are a few exceptions to the building-up order
prediction for the ground state.
Chromium (Z=24) and copper (Z=29) have been found
by experiment to have the following ground-state
electron configurations:
Expected
Cr = [Ar]4s23d4
Cu = [Ar]4s23d9

Found experimentally
Cr = [Ar]4s13d5
Cu = [Ar]4s13d10

When it does this it becomes either a half fullshell (Cr) or a full one (Cu) this results in a
more stable compound with lower energy. It only works if by removing and one electron
from the s subshell an a half full or full subshell results.
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H
He
Li
Be
B
C
N
O
F
Ne
Na
Mg
Al
Si
P
S
Cl
Ar
K
Ca
Sc
Ti
V
Cr
Mn
Fe
Co
Ni
Cu
Zn

1s1
ELECTRONIC
1s2
CONFIGURATIONS
1s2 2s1
OF ELEMENTS 1-30
1s2 2s2
1s2 2s2 2p1
1s2 2s2 2p2
1s2 2s2 2p3
1s2 2s2 2p4
1s2 2s2 2p5
1s2 2s2 2p6
1s2 2s2 2p6 3s1
1s2 2s2 2p6 3s2
1s2 2s2 2p6 3s2 3p1
1s2 2s2 2p6 3s2 3p2
1s2 2s2 2p6 3s2 3p3
1s2 2s2 2p6 3s2 3p4
1s2 2s2 2p6 3s2 3p5
1s2 2s2 2p6 3s2 3p6
1s2 2s2 2p6 3s2 3p6 4s1
1s2 2s2 2p6 3s2 3p6 4s2
1s2 2s2 2p6 3s2 3p6 4s2 3d1
1s2 2s2 2p6 3s2 3p6 4s2 3d2
1s2 2s2 2p6 3s2 3p6 4s2 3d3
1s2 2s2 2p6 3s2 3p6 4s1 3d5
1s2 2s2 2p6 3s2 3p6 4s2 3d5
1s2 2s2 2p6 3s2 3p6 4s2 3d6
1s2 2s2 2p6 3s2 3p6 4s2 3d7
1s2 2s2 2p6 3s2 3p6 4s2 3d8
1s2 2s2 2p6 3s2 3p6 4s1 3d10
1s2 2s2 2p6 3s2 3p6 4s2 3d10

Properties and Electron Configuration

ELECTRONIC CONFIGURATION OF IONS


Positive ions (cations) are formed by removing electrons from atoms
Negative ions (anions) are formed by adding electrons to atoms
Electrons are removed first from the highest occupied orbitals (EXC. transition metals)

SODIUM

CHLORINE

Na

1s2 2s2 2p6 3s1

Na+

1s2 2s2 2p6

Cl

1s2 2s2 2p6 3s2 3p5

Cl

1s2 2s2 2p6 3s2 3p6

Group 1a atom: [Noble gas] ns1

1 electron removed from the 3s orbital

1 electron added to the 3p orbital

-1 eGroup 1a ion+: [Noble gas]

Group 2a atom: [Noble gas] ns2

-2 e-

Group 2a ion2+: [Noble gas]

Positive ions (cations) are formed by removing electrons from atoms

Negative ions (anions) are formed by adding electrons to atoms


Electrons are removed first from the highest occupied orbitals (EXC. transition metals)

SODIUM

CHLORINE

Na

1s2 2s2 2p6 3s1

Na+

1s2 2s2 2p6

Cl

1s2 2s2 2p6 3s2 3p5

Cl

1s2 2s2 2p6 3s2 3p6

1 electron removed from the 3s orbital

1 electron added to the 3p orbital

Group 6a atom: [Noble gas] ns2 np4

+2 e-

Group 6a ion2-: [Noble gas] ns2 np6


Group 7a atom: [Noble gas] ns2 np5

+1 e-

Group 7a ion-: [Noble gas] ns2 np6


Chapter 6/33

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Electron Configurations of Ions


Positive ions (cations) are formed by removing electrons from atoms
Negative ions (anions) are formed by adding electrons to atoms
Electrons are removed first from the highest occupied orbitals (EXC. transition metals)

Atoms

Ions

Fe: [Ar] 4s2 3d6

- 2 e-

Fe2+: [Ar] 3d6

Fe: [Ar] 4s2 3d6

- 3 e-

Fe3+: [Ar] 3d5

FIRST ROW TRANSITION METALS


Despite being of lower energy and being filled first, electrons in the 4s orbital
are removed before any electrons in the 3d orbitals.
TITANIUM

Ti
Ti+
Ti2+
Ti3+
Ti4+

1s2 2s2 2p6 3s2 3p6 4s2 3d2


1s2 2s2 2p6 3s2 3p6 4s1 3d2
1s2 2s2 2p6 3s2 3p6 3d2
1s2 2s2 2p6 3s2 3p6 3d1
1s2 2s2 2p6 3s2 3p6

Electron Configurations of Transition


Metal Cations in Their Ground State
When transition metals form cations, the first
electrons removed are the valence electrons, even
though other electrons were added after.
Electrons may also be removed from the sublevel
closest to the valence shell after the valence
electrons.
The iron atom has two valence electrons:
Fe atom = 1s22s22p63s23p64s23d6

When iron forms a cation, it first loses its valence


electrons:
Fe2+ cation = 1s22s22p63s23p63d6

It can then lose 3d electrons:


Fe3+ cation = 1s22s22p63s23p63d5
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Octet Rule
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 electron configuration with filled s and p sublevels in their
valence electron shell.

An octet
means 8 valence electrons.
is associated with the stability of the noble gases.
Exception:
Helium (He) is stable with 2 valence electrons.
Electron level arrangement

He 2

valence electrons
2

Ne 2, 8

Ar

2, 8, 8

Kr 2, 8, 18, 8

Metals Form Positive Ions


Metals form positive ions
by a loss of their valence electrons.
with the electron configuration of the
nearest noble gas.
that have fewer electrons than
protons.
Group 1A metals ion 1+
Group 2A metals ion 2+
Group 3A metals ion 3+
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37

Formation of a Sodium Ion, Na+


Sodium achieves an octet by losing its one valence
electron.

2, 8, 1

2, 8
38

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Learning Check - Aluminum


A. The number of valence electrons in aluminum is
1) 1e-.
2) 2e-.
3) 3e-.
B. The change in electrons for octet requires a
1) loss of 3e-.
2) gain of 3e-.
3) a gain of 5e-.
C. The ionic charge of aluminum is
1) 3-.
2) 5-.

3) 3+.

D. The symbol for the aluminum ion is


1) Al3+.
2) Al3-.
3) Al+.
39

Formation of Negative Ions


In ionic compounds, nonmetals
achieve an octet arrangement.
gain electrons.
form negatively charged ions with 3-, 2-, or 1charges.

40

Formation of a Chloride, ClChlorine achieves an octet by adding an electron to its


valence electrons.

2, 8, 7

2, 8, 8

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41

Electron Configurations of Ions


Matching Oxidation Number

Chapter 6/42

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Example 8.6 Electron Configurations and Magnetic Properties for Ions


Write the electron configuration and orbital diagram for each ion and determine whether each is diamagnetic or
paramagnetic.
a. Al3+
b. S2
c. Fe3+

Solution
a. Al3+
Begin by writing the electron configuration of the neutral atom. Since this ion has a 3+ charge, remove three
electrons to write the electron configuration of the ion. Write the orbital diagram by drawing half-arrows to
represent each electron in boxes representing the orbitals. Because there are no unpaired electrons, Al 3+ is
diamagnetic.
Al
Al3+

[Ne] 3s2 3p1


[Ne] or [He] 2s2 2p6

Diamagnetic
Continued
b. S2
Write the orbital diagram by drawing half-arrows to represent each electron in boxes representing the
orbitals. Because there are no unpaired electrons, S2 is diamagnetic.
S
S2

[Ne] 3s2 3p4


[Ne] 3s2 3p6

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Nivaldo J. Tro

Diamagnetic

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Example 8.6 Electron Configurations and Magnetic Properties for Ions


Continued
c. Fe3+
Begin by writing the electron configuration of the neutral atom. Since this ion has a 3+ charge, remove three
electrons to write the electron configuration of the ion. Since it is a transition metal, remove the electrons
from the 4s orbital before removing electrons from the 3d orbitals. Write the orbital diagram by drawing halfarrows to represent each electron in boxes representing the orbitals. There are unpaired electrons, so Fe 3+ is
paramagnetic.
Fe
Fe3+

[Ar] 4s2 3d6


[Ar] 4s0 3d5

Paramagnetic

Chemistry: A Molecular Approach, 3rd Edition


Nivaldo J. Tro

2014 Pearson Education, Inc.

Chapter 8. Periodic Properties of the Element

Modified by Dr. Cheng-Yu Lai

1. Atomic Radius
Definition: Half of the distance between
nuclei in covalently bonded diatomic
molecule

Radius decreases across a period


Increased effective nuclear charge due to
decreased shielding
Radius increases down a group
Each row on the periodic table adds a
shell or energy level to the atom

Table of
Atomic
Radii

Cation Formation
Effective nuclear
charge on remaining
electrons increases.

Na atom

1 valence electron

11p+

Valence elost in ion


formation

Result: a smaller
sodium cation, Na+

Remaining e- are
pulled in closer to
the nucleus. Ionic
size decreases.

Anion Formation
Chlorine
atom with 7
valence e17p+

One e- is added
to the outer
shell.
Effective nuclear charge is
reduced and the e- cloud
expands.

A chloride ion is
produced. It is
larger than the
original atom.

Ionic Radii

Isoelectronic = same electron configuration

2. Ionization Energy
Ionization Energy (Ei): The amount of energy
necessary to remove the highest-energy electron
from an isolated neutral atom in the gaseous state

The energy required is called the first ionization energy.


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Chapter 6/53

Ionization Energy
The energy required to remove an electron from an
atom is ionization energy. (measured in kilojoules,
kJ) The energy required is called the first ionization energy.
X(g) + energy X+ + e-

The larger the atom is, the easier its electrons are to
remove.
Ionization energy and atomic radius are inversely
proportional.
Ionization energy is always endothermic, that is
energy is added to the atom to remove the electron.
Chemistry: A Molecular Approach, 3rd Edition
Nivaldo J. Tro

2014 Pearson Education, Inc.

Higher Ionization Energies


M + energy

M+ + e -

M+ + energy

M2+ + e-

M2+ + energy

M3+ + e-

# OF VALENCE LECTRONS 2S1

2S2 2S3 2S4 2S5 2S6 2S7 2S8

Ionization Energy

Worked Example 6.2 Higher Ionization Energies

Instructor Resource DVD for Chemistry, 6th Edition


John McMurry & Robert C. Fay

2012 Pearson Education, Inc.

3. Electron Affinity - EA

Energy is released when an neutral atom gains


an electron.
Gas state
M(g) + 1e M1(g) + EA

Electron affinity is defined as exothermic (),


The more energy that is released, the larger the
electron affinity.
The more negative the number, the larger the EA.

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Electron Affinity
Definition - the energy change associated
with the addition of an electron
Affinity tends to increase across a period
Affinity tends to decrease as you go
down in a period
Electrons farther from the nucleus
experience less nuclear attraction
Some irregularities due to repulsive
forces in the relatively small p
orbitals

Electron Affinity
Definition - the energy change associated
with the addition of an electron

4. Metallic Character
Metallic character is how closely an elements
properties match the ideal properties of a metal.
More malleable and ductile, better conductors, and easier
to ionize

Metallic character decreases left to right across a


period.
Metals found at the left of the period and nonmetals to
the right

Metallic character increases down the column.


Nonmetals found at the top of the middle main group elements
and metals found at the bottom

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Metallic Character in the Periodic


Table

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5. Electronegativity
Electronegativity is a measure of an atoms

attraction for another atoms electrons.


It is an arbitrary scale that ranges from 0 to 4.
The units of electronegativity are Paulings.
Generally, metals are electron givers and have
low electronegativities.
Nonmetals are are electron takers and have
high electronegativities.

The electron affinity is to attract any electron. The electronegativity is


to attract the electrons in a covalent bond between that atom and
another.

Summary of Trends

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