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Unit 2

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Unit 2

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02

Periodic table.
Periodic
properties of
elements

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History - Dmitri Mendeléyev
 The idea that the elements were subjected to some
kind of periodicity was described by the early 18th
century
In 1869, Dmitri Mendeléyev (Mendeleev/Mendeleiv)
proposed his model of periodic table (book: The
Principles of Chemistry), which described elements
according to both their atomic weight and chemical
behaviour
He placed on his table the 63 identified elements
and predicted the discovery of several more
He postulated that:
 The elements, if arranged by atomic mass,
will show an apparent periodicity of
properties
 Elements with similar chemical properties
increase their atomic weight by regular
patterns
 The most frequent elements seem to be
small
 The missing elements’ atomic weight and
properties can be foretold if the contiguous
elements have been identified and described
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Periodic Table

Groups or families: columns

Periods:
rows

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Classification of elements
Metals: easily form positive ions (cations) Non-metals: easily form negative
ions (anions)
Metalloids: intermediate between metals
and non-metals Noble Gases: no reactive

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Periodic table

Elements arranged by their atomic Elements arranged by their


numbers electron configuration

Z= Num. protons = Num. electrons (ns np nd…)

The elements of a group (column) have the identical number of electrons


in the outermost shell, distributed across orbitals of the same shape

Same electron configuration: same number and type of valence electrons.

Same physical and chemical behaviour/properties

The importance and usefulness of the periodic table lies in the fact that
the properties of any element can be accurately predicted knowing its
electronic configuration.

EXERCISE: Do isotopes of an element have the same chemical properties?

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Valence electron shells

EXERCISE: An atom of a certain element has 15 electrons.


What is the ground-state electron configuration of the element?
How should the element be classified?

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Periodic clasification of elements
According to the type of subshell being filled (valence electronic configuration), the
elements can be divided into these categories:
 representative or main group elements: groups 1A-7A (incompletely filled ns or np)
 noble gases: group 8A (completely filled ns2 or np6)
 transition elements (or transition metals): groups 3B-8B, 1B, “2B” (incompletely
filled nd)
 lanthanides and actinides: called f-block transition elements (incompletely filled nf)

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Representative elements – Group 1A (Alkali metals)
and 2A (Alkaline earth metals)

*Images by periodictable.com

Group 1A ns1 tend to lose 1e- to form cations X+

Group 2A ns2 tend to lose 2e- to form cations X2+

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Representative elements – Group 6A (Halogens) and
7A (Oxygen family)

*Images by periodictable.com

Group 6A ns2 np4 tend to gain 2e- to form anions X2-

Group 7A ns2 np5 tend to gain 1e- to form anions X-

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Representative elements – Group 3A (Boron group),
group 4A (Carbon group) and 5A (Nitrogen group)

Group 3A ns2 np1

Group 4A ns2 np2

Group 5A ns2 np3

*Images by
periodictable.com

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Noble Gases – Group 8A

*Images by periodictable.com
* Rn is radioactive and impossible to
photograph (invisible in all conditions)

*Images by smart-elements.com

Group 8A ns2 np6 highly unreactive

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Transition metals – Groups 1B to 8B

*Images by periodictable.com
*Technetium is radioactive

Groups B Incomplete nd subshells

*Group 2B Zn, Cd and Hg are neither transition


metals or representative elements

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Lanthanides, actinides and synthetic elements

Lanthanides and actidinides Incomplete nf subshells

Synthetic elements 95-118

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Curiosities about elements Num of isotopes
Most abundant  Tin – 10 (all stable, highest of naturals)
In the universe  Xenon – 9 (7 stable + 2 unstable)

Shortest & longest half-lives


 Hydrogen 75%
 124Xe - 1.8 · 1022 y
 Helium 23%
 247Cm - 1.56 · 107 y (longest synthetic)
 Oxygen 0.085%
 223Fr - 22 min (shortest natural)

 294Og - 690 μs = 0.69 · 10-3 s

On Earth

 Oxygen 47%
 Silicon 28%
 Aluminium 8%

Bioelements
 Oxygen 65%
 Carbon 19%
 Hydrogen 10%
 Nitrogen 3%

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Electron configuration of cations and anions

Ions Derived from


H: 1s1 H-: 1s2
Representative
O: 1s2 2s2 2p4 O-2: 1s2 2s2 2p6
Elements
Analogue to
the neutral
species
Mn: 1s2 2s2 2p6 3s2 3p6 4s2 3d5
Ions Derived from
Transition Metals
Mn2+: 1s2 2s2 2p6 3s2 3p6 4s0 3d5

In transition metals, electrons are (n-1)d orbitals are more stable


always removed first from the ns than the ns orbital in transition
orbital and then from the (n-1)d orbitals metal ions

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Periodic properties

 Effective Nuclear
Charge
 Atomic Radius
 Ionic Radius
 Ionization Energy
 Electron Affinity
 Metallic Character
 Electronegativity
 Reactivity

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Effective Nuclear Charge
The effective nuclear charge (Zeff) is the nuclear charge felt by an electron
when both the actual nuclear charge (Z) and the repulsive effects (shielding) of
the other electrons are considered.

Zeff = Z - σ σ = shielding constant

The electrons located in the outer shells are protected (shielded) by the
electrons in the inner shells

The electrostatic attraction between a given electron and the positively charged
protons in the nucleus is reduced by electrons in lower shells

Zeff tendency

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Atomic Radius
The atomic radius is the total distance from an atom’s nucleus
to the outermost orbital of electrons (valence electrons)

Tendency

 Group: increases moving down


the group
There are more outer shells
ocuppied, so the distance from the
nucleus to the valence e- is greater.

 Period: increases as the atomic


number decreases
Same shell (n) but higher effective
nuclear charge from left to right.
The valence electrons are more
strongly attracted by the nucleus EXERCISE: arrange the following
and the radius decreases. atoms in order of increasing
atomic radius: P, Si, N.

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Ionic Radius
 The ionic radius is the radius of a cation or an anion.

 When a neutral atom becomes an ion, a change in size is expected

Cationic radius (X+): The radius


decreases over the atomic radius
because it reduces electron-electron
repulsion, but the nuclear charge
remains the same. The electron
cloud shrinks and the cation is
smaller than the atom.

Anionic radius (X-): The radius


increases over the atomic radius,
because the nuclear charge remains
the same but the repulsion resulting
from the additional electrons
enlarges the domain of the
electron cloud.

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Ionic Radius
Isoelectronic cations: Species with the same electron configuration (= num e-)

M3+ M2+ M+

Example
Al Mg Na
1s22s22p63s23p1 1s22s22p63s2 1s22s22p63s1

Al3+ < Mg2+ < Na+

Al3+ Mg2+ Na+


1s22s22p6 1s22s22p6 1s22s22p6

EXERCISE: How EXERCISE: Identify the spheres shown here


would you expect with each of the following ions: S2-, Mg2+, F-, Na+.
the trend for
isoelectronic
anions?

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Ionization Energy
The ionization energy is the minimum energy required to remove a valence
electron from a gaseous atom in its ground state how “tightly” the
electron is held in the atom

Tendency

 Group: decreases moving down the


group
Ionization energy decreases as the
atomic radius increases. The e- in
the outer shell is further from the
nucleus and less attracted (easier to
remove).

 Period: increases from left to right.


As the effective nuclear charge
increase, it is more difficult to remove *High ionization energy means that
an e- (more energy is needed). the e- in the atom is very stable.

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Ionization Energy

First Ionization Energy: energy required to remove the 1st e- from the atom
in its ground state.
E+X X+ + e -

Second Ionization Energy: energy required to remove the 2nd e- from the atom
(cation X+).
E + X+ X2+ + e-

When an e- is removed from an atom, the repulsion between the remaining


electrons decreases. Because the nuclear charge remains constant, more
energy is needed to remove another electron from the positively charged ion.

I1 < I2 < I3 …..

IRREGULARITIES
▪ Group 2A and 3A elements ▪ Group 5A and 6A elements
np1 e- is np4 proximity
Group 2A Group 3A shielded of two e- in
Group 5A Group 6A the same
by ns2
orbital results
( ns2 ) ( ns2 np1 ) complete
( ns2 np3) ( ns2 np4 )
shell in higher
electrostatic
Increases IE Increases IE repulsion

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Electronic Affinity
The electronic affinity is the energy change that occurs when an electron is
accepted by an atom in the gaseous state to form an anion ability to
accept one or more electrons
X (g) + e- X- (g)

Example
F (g) + e- F- (g) ΔH = -328 kJ/mol EA = 328 kJ/mol

*The more positive the electron affinity of an element,


the greater the tendency to accept an electron

 Same tendency as Ionization


Energy
 General correlation between
Electron Affinity and effective
nuclear charge

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Electronic Affinity
 Group: decreases moving down the group.
Electron Affinity decreases with increasing the atomic radius, the e- in the
outer shell is less attracted to the nucleus and less stable. Less tendency to
accept an e- in bigger atoms.
Electron affinity values vary little within a given group.

 Period: increases from left to right.


Electron Affinity decreases with increasing nuclear charge, the e- in the outer
shell is more attracted to the nucleus and feels more comfortable. More
tendency to accept an e-.

IRREGULARITIES
▪ Group 1A and 2A elements ▪ Group 4A and 5A elements

EXERCISE: Which element has a higher first ionization energy and


electron affinity? N or P; K or Ca.

Asign the first ionization energy values.


IE = 1400 kJ/mol; 1012 kJ/mol, 589 kJ/mol; 419 kJ/mol

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Metallic Character
The metallic character is the name given to the set of chemical properties
associated with elements that are metals.

 Metallic elements: lose e- easily/low tendency to gain e- Form cations+

 Non-Metallic elements: gain e- easily/low tendency to lose e- Form anions-

* The metallic character is


related to the ionization
energy and electron affinity
(tendency to lose e-)

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Metallic Character

 Reductive Character: tendency to lose e-.


Metals have a high reductive character

 Oxidative Character: tendency to gain e-.


Non-metals have a high oxidative character

More oxidative character

More reductive character

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Electronegativity
Electronegativity is a measure of the tendency of an atom to attract a bonding
pair of electrons.

 Group: decreases moving down the group


It decreases with increasing atomic number and increasing metallic character.

 Period: increases from left to right.


It increases as the metallic character of the elements decreases.

*Electronegativity is related to electron affinity and ionization energy

High EA
(gain e- easily)
F:
High EN High IE
(retain e-)

Low EA
(gain e- with
Na: difficulty)
Low EN Low IE
(lose e- easily)

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Reactivity
Metallic elements: Non-Metallic elements:
tend to lose e- in a reaction. tend to gain e- in a reaction.

The tendency to lose e- increases The tendency to gain e- increases


as the ionization energy decreases as the electronegativity increases

Metals are more reactive when Non-Metals are more reactive


the IE is lower when the EN is higher

Reactivity tendency Reactivity tendency

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Summary of Periodic Properties  Higher Zeff
 Small atomic radius
 High ionization energy
 High electronic affinity
 High electronegativity
 More oxidative character
 Tendency to gain e-
 Anion formation

 Lower Zeff *Image by sciencenotes.org/


 Big atomic radius
 Low ionization energy
 Low electronic affinity
 Low electronegativity
 More reductive character
 Tendency to lose e-
 Cation formation
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Thank you for
your attention!

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