CHEMICAL PERIODICITY

Alvan F. Shalas, M.Farm., Apt

 HISTORY

1869
The tabulations were
surprisingly similar.
Both emphasized the
Dmitri Mendeleev
(1834–1907) periodicity, or regular
periodic repetition, of
properties with
increasing atomic
weight
 HISTORY
• Mendeleev arranged the known
elements in order of increasing
atomic weight in successive
sequences so that elements
with similar chemical properties
fell into the same column.
• He noted that both physical and
chemical properties of the
elements vary in a periodic
fashion with atomic weight
• It provided for elements that
were unknown at the time
HISTORY
 THE PERIODIC LAW
“The properties of the elements are periodic functions of their
atomic numbers”
GROUP
Elements within a period
have properties that
PERIOD change progressively
across the table

Elements in a group have

similar chemical and physical
properties
PERIODIC TABLE
 PERIODIC TABLE

• Metallic character increases from top to bottom and decreases from left to right
with respect to position in the periodic table
• Nonmetallic character decreases from top to bottom and increases from left to right
in the periodic table.
 ELECTRON CONFIGURATION
QUANTUM NUMBERS
1. The principal quantum number (n) describes the main energy level, or shell, that an electron
occupies. It may be any positive integer:
n = 1, 2, 3, 4, . . .
2. The angular momentum quantum number (l) sublevel, subshell, or specific shape of atomic orbital
that an electron may occupy. This number, ,, may take integral values from 0 up to and including (n - 1):
l = 0, 1, 2, . . . ,(n - 1)
• Thus, the maximum value of l is (n - 1). Each letter corresponds to a different sublevel (subshell) and a
differently shaped orbital:
L = 0, 1, 2, 3, . . . , (n - 1)
s p d f
• In the first shell, the maximum value of l is zero, which tells us that there is only an s subshell and no p
subshell. In the second shell, the permissible values of l are 0 and 1, which tells us that there are only
s and p subshells.
 ELECTRON CONFIGURATION
QUANTUM NUMBERS
3. The magnetic quantum number, (ml) , designates a specific orbital
within a subshell. Within each subshell, ml may take any integral values
from -l, through zero up to and including +l :
ml = (-l), . . . , 0, . . . , (+l)
• The maximum value of ml depends on the value of l.
• For example, when l = 1, which designates the p subshell, there are three
permissible values of ml : -1, 0, and +1.
• Thus, three distinct regions of space, called atomic orbitals, are associated
with a p subshell. We refer to these orbitals as the px, py, and pz orbitals
 ELECTRON CONFIGURATION
QUANTUM NUMBERS
•4.  The spin quantum number (ms) refers to the spin of an electron and
the orientation of the magnetic field produced by this spin.
• For every set of n, l, and ml values, ms can take the value + or -
ms = + ; -
 PERIODIC TABLE
AND ELECTRON CONFIGURATION
• The usual order of filling (Aufbau order) of the orbitals of an
atom. The relative energies are different for different
elements, but the following main features should be noted:
1. The largest energy gap is between the 1s and 2s
orbitals.
2. The energies of orbitals are generally closer together at
higher energies.
3. The gap between np and (n + 1 )s (e.g., between 2p and
3s or between 3p and 4s) is fairly large.
4. The gap between (n - 1 )d and ns (e.g., between 3d and
4s) is quite small.
5. The gap between (n - 2 )f and ns (e.g., between 4f and
6s) is even smaller
 PERIODIC TABLE
AND ELECTRON CONFIGURATION
An aid to remembering the usual order of filling
of atomic orbitals.
• Write each shell (value of n) on one
horizontal line, starting with n = 1 at the
bottom.
• Write all like subshells (same l values) in the
same vertical column.
• Subshells are filled in order of increasing (n
+ l ) . When subshells have the same (n + l ),
the subshell with the lower n fills first.
• To use the diagram, we follow the diagonal
arrows in order, reading bottom to top.
 ATOMIC ORBITALS
s ORBITAL
 ATOMIC ORBITALS
p ORBITAL
 ATOMIC ORBITALS
d ORBITAL
 ATOMIC ORBITALS
f ORBITAL
 ELECTRON CONFIGURATION
QUANTUM NUMBERS
 PERIODIC TABLE
AND ELECTRON CONFIGURATION
• The A groups contain elements in which s
and p orbitals are being filled.
• Elements within any particular A group
have similar electron configurations and
chemical properties
• The B groups include the transition metals
in which there are one or two electrons in
the s orbital of the outermost occupied
shell, and the d orbitals, one shell
smaller, are being filled.
• There are some more irregularities in the
B groups below the fourth period. In the
heavier B group elements, the higher
energy subshells in different principal
shells have energies that are very nearly
equal. It is easy for an electron to jump
from one orbital to another of nearly the
same energy, even in a different set. This
is because the orbital energies are
 PERIODIC TABLE
AND ELECTRON CONFIGURATION

1. Determine the electron configurations of (a) magnesium (Mg); and

(b) molybdenum (Mo)!

(a)[Ne] 3s2
(b)[Kr] 5s1 4d5
 PERIODIC PROPERTIES of THE
ELEMENTS
1. ATOM
RADII
Atomic radii are often
stated in angstroms (1
Å = 10-10 m) or in the SI
units nanometers (1 nm
= 10-9 m) or picometers
( 1pm = 10 -12 m)

• Atomic radii increase going down a group because

electrons are being added to shells farther from the
nucleus.
• Atomic radii decrease from left to right within a given
period owing to increasing effective nuclear charge.
• Hydrogen atoms are the smallest and cesium atoms are
the largest naturally occurring atoms.
 PERIODIC PROPERTIES of THE
ELEMENTS
2. IONIZATION ENERGY
• The first ionization energy (IE1) (first ionization potential):
“The minimum amount of energy required to remove the most loosely
bound electron from an isolated gaseous atom to form an ion with a 1+
charge”

• The second ionization energy (IE2 )

“The amount of energy required to remove the second electron”
 PERIODIC PROPERTIES of THE
ELEMENTS

• A plot of first ionization energies for the first 38 elements

versus atomic number. The noble gases have very high first
ionization energies, and the 1A metals have low first
ionization energies.
• Note the similarities in the variations for the Period 2
elements, 3 through 10, to those for the Period 3 elements,
11 through 18, as well as for the later A group elements
 PERIODIC PROPERTIES of THE
ELEMENTS
Exceptions :
• The first ionization energies for the Group 3A elements (B, Al, Ga, In,
Tl) are exceptions to the general horizontal trends.
• They are lower than those of the 2A elements in the same periods
because the 3A elements have only a single electron in their
outermost p orbitals.
• Less energy is required to remove the first p electron than the second
s electron from the outermost shell because the p orbital is at a
higher energy (less stable) than an s orbital within the same shell (n
value).
 PERIODIC PROPERTIES of THE
ELEMENTS
Exceptions :
• Group 6A elements (O, S, Se, Te, Po).
• This group behavior is because the fourth np electron in the Group 6A
elements is paired with another electron in the same orbital
• So it experiences greater repulsion than it would in an orbital by itself.
• This increased repulsion outweighs the increase in Zeff, so the fourth
np electron in an outer shell (Group 6A elements) is somewhat easier
to remove (lower ionization energy) than is the third np electron in an
outer shell (Group 5A elements)
 PERIODIC PROPERTIES of THE
ELEMENTS
3. ELECTRON AFFINITY
• Electron affinity (EA):
“The energy change when an electron is added to an isolated gaseous
atom to form an ion with a 1- charge.
Helium will not add an electron

When one mole of gaseous chlorine atoms gain one electron

each to form gaseous chloride ions, 349 kJ of energy is released
(exothermic).
Elements with very negative electron affinities gain electrons easily to form negative ions (anions)
 PERIODIC PROPERTIES of THE
ELEMENTS
3. ELECTRON AFFINITY

• A plot of electron affinity versus atomic

number for the first 20 elements. The
general horizontal trend is that electron
affinities become more negative (more
energy is released as an extra electron is
added) from Group 1A through Group 7A
for a given period.
• Exceptions occur at the 2A and 5A
 PERIODIC PROPERTIES of THE
ELEMENTS
Exceptions :
• The elements of Groups 2A and 5A, which have less negative values
than the trends suggest.
• It is very difficult to add an electron to a 2A metal atom because its
outer s subshell is filled.
• The values for the 5A elements are slightly less negative than
expected because they apply to the addition of an electron to a half-
filled set of np orbitals (ns2np3 - ns2np4), which requires pairing. The
resulting repulsion overcomes the increased attractive force of the
nucleus
 PERIODIC PROPERTIES of THE
ELEMENTS
4. IONIC RADII
 PERIODIC PROPERTIES of THE
ELEMENTS
4. IONIC RADII
1. Simple positively charged ions (cations) are always smaller than the
neutral atoms from which they are formed.
2. Simple negatively charged ions (anions) are always larger than the
neutral atoms from which they are formed.
3. Both cation and anion sizes increase going down a group.
4. Within an isoelectronic series, radii decrease with increasing atomic
number because of increasing nuclear charge.
 PERIODIC PROPERTIES of THE
ELEMENTS
4. IONIC RADII

Isoelectronic species have the same number of electrons

 PERIODIC PROPERTIES of THE
ELEMENTS
5.
ELECTRONEGATIVITY
• The electronegativity (EN) of an element:

“A measure of the relative tendency of an atom to attract electrons to

itself when it is chemically combined with another atom”
 PERIODIC PROPERTIES of THE
ELEMENTS
5.
ELECTRONEGATIVITY
TERIMA KASIH