PERIODIC TABLE

Periodic Table
• Aufbau Building up Principle
• Pauli’s Exclusion Principle
• Hund’s Rule of Maximum Multiplicity
• Multiplicity – number of unpaired electron
plus 1 or the number of possible energy
levels that depend on the orientation of the
net magnetic moment in a magnetic field
 Atom Electron Configurations
Increasing (n + l), then increasing n
l value
n value
0 1 2 3
8 8s
8s

7 7s
7s 7p
7p

6s
6s 6p
6 6p 6d
6d
5s
5s 5p 5d 5f5f
5 5p 5d
n+l=8
4s
4s 4p 4d 4f4f
4 4p 4d
n+l=6 n+l=7
3s
3s 3p 3d
3 3p 3d
n+l=4 n+l=5
2s
2s 2p
2 2p
n+l=2 n+ l=3
1s
1s
1 n+l=1
1s
Atom Electron Configurations 1s
2s 2p

3s 3p

4 s 3d 3d 4p

5 s 4d 4d 5p

6 s 5d 4f 5d 6p

7 s 6d 5f 6d 7p

Main group Lanthanides and actinides Transition elements Main group

s block f block d block p block

Block identities show where successive e- add.

Note: d “steps down”, f “steps down” again.
Elements with Deviation of Electronic
Configuration:
• Cr 24 [Ar] 4s13d5
• Cu 29 [Ar]4s13d10
• Nb 41 [Kr] 5s14d4
• Mo 42 [Kr]5s14d5
• Ru 44 [Kr]5s14d7
• Rh 45 [Kr]5s14d8
• Pd 46 [Kr] 4d10
• Ag 47 [Kr]5s14d10
• La 57 [Xe]6s25d1
• Ce 58 [Xe] 6s24f15d1
• Gd 64 [Xe] 6s24f75d1
• Pt 78 [Xe]6s14f145d9
• Au 79 [Xe]6s14f145d10
• Ac 89 [Rn] 7s2 6d1
• Th 90 [Rn] 7s2 6d2
• Pa 91 [Rn] 7s2 5f2 6d1
•U 92 [Rn] 7s2 5f3 6d1
• Np 93 [Rn] 7s2 5f4 6d1
• Cm 96 [Rn] 7s2 5f7 6d1
• Cf 98 [Rn] 7s2 5f9 6d1
• Ds 110 [Rn] 7s1 5f14 6d10
 Paramagnetism & Unpaired Electrons
Spinning e- = tiny magnet. If all e- are paired:
 The magnets cancel.
 The atom is diamagnetic
• pushed weakly away from magnetic fields.

With unpaired e-:

 Unpaired spins point in the same direction (Hund’s rule).
 Magnets add.
 The atom is paramagnetic.
• attracted to magnetic fields.

If individual atom-magnets line up in a bulk sample

 A ferromagnet - a permanent magnet. Ex. Fe, Ni, Co
Paramagnetism & Unpaired
Electrons
Paramagnet Ferromagnet
 Factors Affecting Atomic Orbital Energies

The Effect of Nuclear Charge (Zeffective)

Higher nuclear charge lowers orbital energy (stabilizes the system)
by increasing nucleus-electron attractions.

The Effect of Electron Repulsions (Shielding)

Additional electron in the same orbital

An additional electron raises the orbital energy through electron-

electron repulsions.

Additional electrons in inner orbitals

Inner electrons shield outer electrons more effectively than do

electrons in the same sublevel.
The effect of nuclear charge on orbital energy.
Shielding
Penetration and Shielding
Slater’s Rule

Zeffective = Z – S

where: Z – nuclear charge

S – Shielding Constant
Determining the shielding constant (S) for a specific
electron:

• The electronic structure of the atom is written in

groupings as follows:
(1s) (2s,2p) (3s,3p) (3d) (4s,4p) (4d) (4f) (5s,5p) etc.
• The electrons in the higher groups (to the right of
the list above) do not shield those in the lower
groups.
• For ns or np valence electrons:
• Electrons in the same ns,np group contribute 0.35,
except the 1s, where 0.30 works better.
• Electrons in the n-1 group contribute 0.85.
• Electrons in the n-2 or lower groups contributes 1.00.
• For nd and nf valence electrons:
• Electrons in the same nd and nf group contribute 0.35.
• Electrons in groups to the left contribute 1.00.
Example
• Determine the Zeffective of the outermost electron in
Oxygen atom.
• Determine the Zeffective of the 3d and 4s electrons of
nickel atom (Z = 28)
• As a result of penetration
and shielding, the order
of energies in many-
electron atoms is
typically:

ns < np < nd < nf

 Periodic Trends: Atomic Radii
• Estimate of atomic size 200 pm
• ½(homonuclear bond length)
• Cl = 100 pm (Cl2 bond = 200 pm)
• H = 37 pm (H2 bond =74 pm)
Cl Cl

100 pm
• Radii are additive.
 HCl has a (37 + 100) = 137 pm bond
 Periodic Trends:
Atoms grow down a group.
Atomic Radii
• Larger shell (larger n) added in each new row.

Atoms shrink across a period

• e- add to the same shell. Increase size? No,
• p+ add to the nucleus.
• Larger charge pulls all e- in, shrinking the atom.

Big Jump from noble gas to alkali metal

• A new shell (with larger n) is added.
Periodic Trends: Atomic Radii
Increasing Size

Increasing Size
Periodicity of atomic radius
 Periodic Trends: Ionic Radii
Group 1A Group 2A Group 3A
Li Li+ Be Be2+ B B3+
152 90 112 59 85 25
Na Na+ Mg Mg2+ Al Al3+
186 116 160 86 143 68
K K+ Ca Ca2+ Ga Ga3+
227 152 197 114 135 76
Rb Rb+ Sr Sr2+ In In3+
248 166 215 132 167 94

A cation is smaller than its neutral atom.

Main block: outer shell completely removed.
e-/e- repulsion reduced (fewer e- ).
 Periodic Trends: Ionic Radii
Group 6A Group 7A
O O2- F F-
73 126 72 119
S S2- Cl Cl-
103 170 100 167
Se Se2- Br Br-
119 184 114 182
Te Te2- I I-
142 207 133 206

An anion is larger than its neutral atom.

More e-/e- repulsion (more e-). The shell swells.
Lanthanide Contraction
• Applicable for elements belonging to Period 6
• The repulsions between electrons being added on
crossing the f-block fail to compensate for the increasing
nuclear charge so Zeff increases from left to right across
a period.

Example:
Molybdenum (Z=42): Atomic radius = 1.40 angstrom
vs
tungsten (Z=74) : Atomic radius = 1.41 angstrom
Polarizability
• Ability of an atom to be distorted by an electric
field (such as that of the neighboring ion
• Large, heavy atoms and ions tends to be highly
polarizable.
 Periodic Trends: Ionization
Energies
Ionization energy (IE)
E to remove an e- from a gas-phase atom.

Mg(g) Mg+(g) + e- ΔE  Ionization Energy

Also called IE1

Down a group: IE ↓. Larger atom = less tightly held e-
Across a period: IE ↑. Smaller atom = more tightly
held e-
Second ionization energy (IE2)
E required to remove a 2nd e- from A+(g).

Mg(g) Mg+ (g) + e- ΔE 

IE1
Mg+(g) Mg2+(g) + e- ΔE  IE2
• IE2 > IE1
• Mg+ holds the 2nd e- more tightly.
• Huge increase if e- removal breaks a complete shell (the
core).
 Periodic Trends: Electron Affinities
Electron Affinity (EA)
E released when an e- adds to a gas-phase atom.

F(g) + e- F-(g) ΔE = Electron Affinity

• Usually exothermic (EA is negative)
• EA increases from left to right.
• Metals have low EA; nonmetals have high EA.
• Some tables list positive numbers.
 a sign-convention choice.
 Periodic Trends: Electron Affinities

Table 7.9 Electron Affinities (kJ/mol)

1A 2A 3A 4A 5A 6A 7A 8A
(1) (2) (13) (14) (15) (16) (17) (18)

H He
-73 >0

Li Be B C N O F Ne
-60 >0 -27 -122 >0 -141 -328 >0
Na Mg Al Si P S Cl Ar
-53 >0 -43 -134 -72 -200 -349 >0
K Ca Ga Ge As Se Br Kr
-48 -2 -30 -119 -78 -195 -325 >0
Rb Sr In Sn Sb Te I Xe
-47 -5 -30 -107 -103 -190 -295 >0
Electron Affinity
Electronegativity
Represented by the symbol  (chi)
It is the power of an atom of the element to
attract electrons to itself when it is part of a
compound.

Many Definition of electronnegativities:

Pauling’s Definition, P
• Relates electronegativity to the energies of bond formation
Mulliken electronegativities, M
M = ½ (I + Ea )
• Allred-Rochow Definition
• Elements with high electronegativity are those with high
effective nuclear charge and small covalent radius
Trends in three atomic properties.
 CONCEPT MAP
ATOMS

Protons Aufbau Principle

Dalton's
Atomic Theory Pauli's Principle
Neutrons

Hund's Rule
Subatomic Atomic
Particles Electrons Periodic Table
Orbitals

Quantum Dualistic
Nature of Schrodinger Wave Periodic trends
Theory
Matter Equation Function
Atomic/Ionic Radius
Quantum Ionization Energy
Numbers Shielding Effect in electrons
Electron Affinity

Electronegativity
Polarizability