EXCEPTIONS TO THE FILLING RULES

Exceptions of the Rules

• Remember, (n – 1)d orbitals are generally filled
after ns orbitals and before np orbitals due to
differences in energies of the electrons

• There are some exceptions to this rule:

• When it is possible to half-fill or fill the (n-1)d shell, the
ns subshell can be left half-filled
• This is an example of Hund’s Rule
• The ns and (n-1)d orbitals are very close in energy, so
the more parallel spins, the better!
Example
4s 3d
Sc [Ar] 4s23d1  
- 4s filled before 3d

4s 3d
Ti [Ar] 4s23d2   

4s 3d

V [Ar] 4s23d3    
 Example
Cr You might expect…
4s 3d
[Ar] 4s23d4     

• Physical properties indicate that this is not the electron

configuration
– It is actually…
4s 3d

Cr [Ar] 4s13d5      

• Notice the 3d subshell is half-filled

• This configuration maximizes unpaired electrons - Hund’s Rule
 Exception to the Rules
• Having a filled subshell is also energetically
favorable, so copper has an unexpected
configuration…
4s 3d

Cu [Ar]3d104s1      

• The energetic stability gained from having either

a filled or a half-filled subshell has an effect on
the reactivity of different elements
 What About Valence Electrons?
• When considering the principal electron shells (n =
1,2,3,…), there are two types of electrons:

• Core Electrons: electrons in the filled “inner”

shell(s) of an atom
• Valence Electrons: electrons in the unfilled “outer”
shell of an atom

• All elements in the same group have similar chemical

properties because they have the same number of
valence electrons in their outer shell!
What Orbitals Correspond to
Valence Electrons Location?
• For elements in the first three periods:
• The core electrons are those in the preceding noble gas
configuration
• The additional electrons in the outer shell are the valence
electrons
• Example:
Full Configuration - B 1s2 2s2 2p1
Noble Gas Config - B [He] 2s2 2p1

Core: 1s2 Valence: 2s2 2p1

(Shell with n = 1) (Shell with n = 2)
 Location of Valence Electrons
• For elements in the fourth period and below in groups
3A – 7A, the filled d subshells are also part of the core,
even though they are not included in the noble gas
configuration

Full Config - Se 1s2 2s2 2p6 3s2 3p6 4s2 3d104p4

Noble Gas Config - Se [Ar] 4s2 3d104p4

Core: Valence:
1s2 2s2 2p6 3s2 3p63d10 4s2 4p4
• ONLY ELECTRONS IN HIGHEST NUMBERED s- AND p-
ORBITALS ARE VALENCE ELECTRONS!