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CHAPTER 4

PERIODIC TABLE

Lecturer:
Nor Fadilah Chayed

Upon completion of this course, students should be able to:


1. Indicate period, group and block (s,p,d,f).
2. Specify the position of metals, metalloids and non-metals.
3. Deduce the position of elements from electronic configuration.
4. Explain the variation in atomic and ionic radii.
5. Explain the radius of isoelectronic species.
6. Define first and second ionization energy and explain the
variations in the first ionization energy across period and down
the group.
7. Define electron affinity and electronegativity.

CLASSIFICATION OF ELEMENTS

Dmitri Mendeleev (1869) and Lothar Meyer proposed the periodic


law:
Elements were arranged based on the regular, periodic
recurrence of properties
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Henry Moseley (1930) discovered the


atomic number which is later used
as the basis for classifying elements
in the Modern Periodic Table.
In the periodic table, the elements are
placed

in

increasing

atomic

number, starting at the upper left and


arranged in a series of horizontal
rows.
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Classification of the Elements

Periodic table and electron configuration


Electron configuration play an important role in the construction

of the periodic table


The order of filling orbitals is as follows:

1s < 2s < 2p < 3s < 3p < 4s < 3d


<4p < 5s < 4d < 5p < 6s < 4f <5d
< 6p < 7s < 5f < 6d < 7p

Categories of Electrons
Inner (core) electrons are those an atom has in common
with the previous noble gas and any completed transition
series.
Outer electrons are those in the highest energy level
(highest n value).
Valence electrons are those involved in forming
compounds.
- For main group elements, the valence electrons are the outer
electrons.
- For transition elements, the valence electrons include the outer
electrons and any (n -1)d electrons.
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Nonmetals are found to the right of the


metalloids.
Metals are found to the left of the
metalloids

Metals located on the


left part of the
1.Classification
according
toperiodic
table
metallic property:
The alkali metals - Group 1A

The alkaline earth metal Group 2A

Non metals are located on the right part


The halogens Group 7A
The Nobel gases Group 8A

Metalloids possess both metallic and non

metallic properties
B, Si, Ge, As, Sb, Te, Po and At
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Parts of Periodic Table


(a) Group
Vertical bars,
Each group consists of elements that have the same number

of valence electrons in their valence (outermost) shells


There are a total of 18 groups from Group1 to Group 18
E.g.

Group 1A (valence electron = 1)


Li (3) :
1s2 2s1
Na (11):
___________
Group 5A (valence electron = 2+3 = 5)
N (7) :
1s2 2s2 2p3
P (15) :
___________
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Elements with similar


properties are organized
in groups or families.

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Electron Configuration and Group


Elements in the same group of the periodic table have the same
outer electron configuration.
Elements in the same group of the periodic table exhibit similar
chemical behavior.
Similar outer electron configurations correlate with similar
chemical behavior.

Potassium reacting with water.

Chlorine reacting with potassium.

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(b) Period
Horizontal bars,
Each period consists of elements that have the same

similar valence shells


E.g.

2nd Period (valence n=2)

Li: 1s2 2s1

3rd Period (valence n=3)

Al: 1s2 2s2 2p6 3s2 3p1

5th Period (valence n=5)

Zr: [Kr] 5s2 4d2

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2. Classification according to valence shell


electron configuration
(i) s-block elements
-Metal (group 1 and 2)
-Half filled s orbital (s1)or fully filled s orbital (s2)in the
valence shell
(ii) p-block elements
-Metals, non-metals and metalloids (group 13-18)
-Valence shell configuration varies from s2p1 to s2p6
(iii) d-block elements
-Metals with electronic configuration varies from s2d1 to s2d10
(iv) f-block elements
-Metals have incomplete f orbital
- Incomplete 4f orbital (The lanthanides)
-Incomplete 5f orbital (Actinides)
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15

ns2np6

ns2np5

ns2np4

ns2np3

ns2np2

ns2np1
d10

d5

d1

ns2

ns1

Ground State Electron Configurations of the Elements

4f
5f
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Electron Configurations of Cations and Anions


of Representative Element
Na : 1s 2s 2p 3s or [Ne] 3s
2

Na : [Ne]
+

Ca : 1s22s22p6 3s23p6 4s2 or [Ar] 4s2 Ca2+: [Ar]


Al :1s22s22p63s23p1 or [Ne]3s23p1

Atoms gain electrons so


that anion has a noblegas outer electron
configuration.

Al3+: [Ne]

Atoms lose
electrons so that
cation has a
noble-gas outer
electron
configuration.

F : 1s22s22p5 F- : 1s22s22p6 or [Ne]


O : 1s22s22p4 O2-: 1s22s22p6 or [Ne]
N : 1s22s22p3 N3- : 1s22s22p6 or [Ne]
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-1

-2

-3

+3

+2

+1

Cations and Anions of Representative Elements

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Electron Configurations of Cations of Transition Metals


When a cation is formed from an atom of a transition metal,
electrons are always removed first from the ns orbital and
then from the (n 1)d orbitals.

Fe:

[Ar]4s23d6

Fe2+: [Ar]4s03d6 or [Ar]3d6

Mn:

[Ar]4s23d5

Mn2+: [Ar]4s03d5 or [Ar]3d5

Fe3+: [Ar]4s03d5 or [Ar]3d5

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Problem 1
Determine the period, block and group for each element with the following
configuration:
A: 1s2 2s2 2p3
B: 1s2 2s2 2p6 3s2 3p6
C: 1s2 2s2 2p6 3s2
D: 1s2 2s2 2p6 3s2 3p6 4s2 3d3
Answer:

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Metallic Behavior
Metallic character decreases across a period (increase non
metallic character) and increase down a group.

On descending a group (downwards), the metallic character


increase:
(i) ionization energy decrease
(ii) reactivity increase.

Metallic bonding is stronger and the melting point is higher if:


1) The ionic size is smaller
2) The number of valence electron is greater
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Trends in metallic behavior

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Periodic Physical
Properties
The periodic law: When elements are arranged in the
periodic table in order of increasing atomic number, a regular
change in the outer electronic configuration and a periodic
variation of properties is observed.
The following physical properties show a periodic trend:
1. Atomic size
2. Ionization energy
3. Electron affinity
4. Electronegativity
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1. Atomic size
The atomic radius
= of the distance between 2 nuclei of two adjacent atoms
=d

Atomic radius of an element is determined by two factor:


Screening effect
Nuclear charge
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Screening effect
The atomic radius increase downwards in a group.
Electrons fill up a new shell downwards. Outer electrons are
shielded from the nucleus by electrons in inner shells
(mutual repulsions between electrons in different shell) and
are less tightly held.

Nucleus charge
The atomic radius decrease towards the right across a
period.
Electrons fill up the same shell, cause the effective nuclear
charge (Zeff) of the atom increases which pulls all electrons
closer to nucleus, thus the electrons are held more tightly.
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Effective nuclear charge (Zeff) is the positive charge


felt by an electron.
Zeff Z
=eff
Z=
- Z -

0 < < Z ( = shielding constant)

Zeff Z number of inner or core electrons


Z

Core

Zeff

Radius

Na

11

10

186

Mg

12

10

160

Al

13

10

143

Si

14

10

132

As the distance
from nucleus
increases,
increases and
Zeff decreases

8.3

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Effective Nuclear Charge (Zeff)

increasing Zeff

increasing Zeff

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8.3

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Atomic radius across d-block elements


d-block elements consist of three series Period 4, 5 and 6
The atomic radii of first row of d-block elements tend to be
approximately constant across the period

Reason:

additional electrons go into inner electron subshell (3d).


At the same time, the number of electrons in the
outermost subshell (4s) remain constant.

3d electrons shield the outer 4s electrons from nuclear


charge more effectively than the outer shell can shield
one another.

Effect of increased nuclear charge cancelled by the


screening effect electron in 3d orbital

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Size of cations

Ionic Radius

Sizes of cations are smaller than their corresponding parent atom .


The atoms lose the valence electrons, leaving electrons of the inner shells which
tend to attract the nucleus more, thus decreasing size.

E.g. Li+ ion < Li atom


Size of anions

Sizes of anions are larger compared to their corresponding parent atom.


The electrons are added into the same shell and tend to repel each other and so
increase size.

E.g. F- ion > F atom


Cation is always smaller than atom from which it is formed.
Anion is always larger than atom from which it is formed.

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Comparison of Atomic Radii with Ionic Radii

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Trends in Atomic Size


Atomic size increases as the principal quantum number n
increases.
- As n increases, the probability that the outer electrons will be farther
from the nucleus increases.

Atomic size decreases as the effective nuclear charge Zeff


increases.
- As Zeff increases, the outer electrons are pulled closer to the nucleus.

For main group elements:


- atomic size increases down a group in the periodic table
and decreases across a period.

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Isoelectronic ions
Isoelectronic: a series of ions or atoms which have the same

number of electrons and same ground-state electron


configuration.
Sizes of the ion/atom decrease as the number of protons
increases.
Reason: higher nuclear charge (protons) are pulling in the
same number of electrons
The larger number of electrons, the greater repulsion between
electrons, the larger ionic or atomic radius.
E.g. 10 electron series: 10Ne>11Na+ >12Mg2+ >13Al3+

Ne : 1s22s22p6

Mg2+ 1s22s22p6 or [Ne]

Al3+: 1s22s22p6 or [Ne]


Na+, Mg2+, Al3+are all isoelectronic with Ne

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Problem 2 : Ranking Elements by Atomic Size


Using only the periodic table (not Figure 8.15), rank each set of maingroup elements in order of decreasing atomic size:
(a) Ca, Mg, Sr

(b) K, Ga, Ca

(c) Br, Rb, Kr

(d) Sr, Ca, Rb

Answer:

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Problem 3: Ranking Ions by Size


Rank each set of ions in order of decreasing size, and explain your
ranking:
(a) Ca2+, Sr2+, Mg2+
PLAN:

(b) K+, S2, Cl

(c) Au+, Au3+

Find the position of each element on the periodic table and


apply the trends for ionic size.

Answer:

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2. Ionization energy
Ionization energy is the minimum energy (kJ/mol)
required to remove an electron from a gaseous atom in its
ground state.
I1 + X (g)

X+(g) + e-

I1 first ionization energy

I2 + X (g)

X2+(g) + e-

I2 second ionization energy

I3 + X (g)

X3+(g) + e-

I3 third ionization energy

I1 < I2 < I3
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First ionization energy = the energy needed to remove 1


mole of the outermost electrons from 1 mole of neutral
atoms in the gas phase
M(g) M+(g) + e-

H1 = +X kJ mol-1

Second ionization energy = energy required to remove 1


mole of electrons from 1 mole of unipositive ions in
gaseous state
M+(g) M2+(g) + e

H2 = +Y kJ mol-1

Factor that affect ionization energy:


Atomic radius
Nuclear charge
Screening effect
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Factor that affect ionization energy:


Atomic radius
Atomic radius increase (distance outer electron from nucleus
increase), the ionization decrease (easy to lose electron).
Nuclear charge
Nuclear charge becomes more positive, attraction on the outer
shell electrons increase, cause ionization energy increase.
Screening effect (repulsion effect)
Valence electron are shielded from the attraction of the nucleus by the
screening effects of the electrons in inner shells.
Lower quantum number (n) have stronger shielding effect.
Radius of positive ion is smaller than its atom, attraction between
nucleus and electrons left become stronger (screening effect decrease).
IE always increase in the order: 1st IE < 2nd IE < 3rd IE..
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Filled n=1 shell


Filled n=2 shell
Filled n=3 shell
Filled n=4 shell
Filled n=5 shell

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General Trend in First Ionization Energies


Increasing First Ionization Energy

Increasing First Ionization Energy

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Problem 4: Ranking Elements by First Ionization Energy


Using the periodic table only, rank the elements in each of the following
sets in order of decreasing IE1:
(a) Kr, He, Ar
(c) K, Ca, Rb

(b) Sb, Te, Sn


(d) I, Xe, Cs

Answer:

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3. Electron affinity

The electron affinity is the energy involved when 1 mole of electrons


is gained (accepted) by 1 mole of neutral atoms in the gas phase.

The process would be represented by the following equation:


X (g) + e- X- (g)

F (g) + e-

F-(g)

HEA = -A kJ mol-1

H = -328 kJ/mol

EA = +328 kJ/mol

The addition of one electron to a neutral atom is exothermic for


nearly all atoms

When an electron is more easily accepted into an atom, more


energy is given off, thus the higher the electron affinity and more ve
is the value of HEA
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Electron affinities of the main-group elements.

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General trend:

EA become less negative (decreases) downwards in the


periodic table

Reason: Electrons are added less easily into the atom


because of the increase in size and there is greater repulsion
from electrons already present

EA become more negative (increases) towards the right


across the period

Reason: Electrons are added more easily into the atom


because of the smaller size

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Trends in three atomic properties.


` Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

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4. Electronegativity

Electronegativity is the ability of the atom in a covalent bond to attracts


pairs of shared electrons to itself.

The higher the electronegativity of an atom, the greater its attraction for
bonding electrons.

Elements with low ionization energies have low electronegativity


(electropositive elements).

Elements with high ionization energies have high electronegativity


(electronegative elements).
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General trend:
In a group (downwards) the electronegativity

decrease.
Reason: Increased distance between the valence
electrons and the nucleus weakens the pull of the
nucleus on the electrons.
The a period (towards the right), the electronegativity

increase.
Reason: Decreased distance between the valence
electrons and the nucleus, thus stronger pull of the
nucleus on the electrons.
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Summary of physical properties


LEFT TO RIGHT
(Across period)

TOP TO BOTTOM
(Down the group)

Atomic Radius

Decreases

Increases

Ionization energy

Increases

Decreases

Electron affinity

Increases
(more ve)

Decreases
(less ve)

Electronegativity

Increases

Decreases

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