Electron Configurations

The content that follows is the substance of General Chemistry Lecture 26. In this lecture we continue the discussion of Quantum Numbers and their use
in Electron Configurations as well as the relationship of electron configuration to the periodic properties of the elements.

Electron Configuration
Electron configurations are the summary of where the electrons are around a nucleus. As we learned earlier, each neutral atom has a number of electrons
equal to its number of protons. What we will do now is place those electrons into an arrangement around the nucleus that indicates their energy and the
shape of the orbital in which they are located. Here is a summary of the types of orbitals and how many electrons each can contain:

So based on what we know about the quantum numbers and using the chart above, you need 2 electrons to fill an s orbital, 6 electrons to fill a p orbital,
10 electrons to fill a d orbital and 14 electrons to fill the f orbital. BUT what we haven't discussed is how these orbitals get filled...the order of fill.

Order of Fill

The order in which electrons are placed into the orbitals is based on the order of their energy. This is referred to as the Aufbau principle. The lowest
energy orbitals fill first. Just like the quantum numbers themselves this order was determined by calculation and is summarized by the following chart:
or you can just use the periodic table:

How to Write an Electron Configuration

The symbols used for writing the electron configuration start with the shell number (n) followed by the type of orbital and finally the superscript indicates
how many electrons are in the orbital.
 

For example:

Looking at the periodic table, you can see that Oxygen has 8 electrons. Based on the order of fill above, these 8 electrons would fill in the following order
1s, 2s and then 2p. So Oxygen's electron configuration would be O 1s22s22p4.

Special Cases

Configurations of ions present a special case of electron configuration and also demonstrate the reason for the formation of those ions in the first place.

If you need to write the full electron configuration for an anion, then you are just adding additional electrons and the configuration is simply continued.

For example, we know that Oxygen always forms 2- ions when it makes an ion. This would add 2 electrons to its normal configuration making the new
configuration: O2- 1s22s22p6. With 10 electrons you should note that oxygen's electron configuration is now exactly the same as Neon's. We talked about
the fact that ions form because they can become more stable with the gain or loss of electrons to become like the noble gases and now you can actually see
how they become the same.

The electron configurations for Cations are also made based on the number of electrons but there is a slight difference in the way they are configured.
First you should write their normal electron configuration and then when you remove electrons you have to take them from the outermost shell. Note that
this is not always the same way they were added.

Here is an example of what I mean:

Iron has 26 electrons so its normal electron configuration would be: Fe 1s22s22p63s23p64s23d6

When we make a 3+ ion for Iron, we need to take the electrons from the outermost shell first so that would be the 4s shell NOT the 3d shell: Fe3+
1s22s22p63s23p63d5

One other note on writing electron configurations: A short cut. When writing some of the lower table configurations the total configuration can be fairly
long. In these cases, you can use the previous noble gas to abbreviate the configuration as shown below. You just have to finish the configuration from
where the noble gas leaves it:

Exceptions

As with every other topic we have covered to date there are exceptions to the order of fill as well. But based on the electron configurations that are
generated, these exceptions are easy to understand.

In the d block, specifically the groups containing Chromium and Copper, there is an exception in how they are filled.

Here are the actual configurations:

In these columns, the 4s and 3d

Practice, Practice, Practice

There are lots of quizzes on electron configurations you can practice with located here

Orbital Diagrams
Another way to represent the order of fill for an atom is by using an orbital diagram often referred to as "the little boxes":

Image result for orbital diagram

The boxes are used to represent the orbitals and to show the electrons placed in them. The order of fill is the same but as you can see from above the
electrons are placed singly into the boxes before filling them with both electrons. This is called Hund's Rule: "Half fill before you Full fill" and again this
rule was established based on energy calculations that indicated that this was the way atoms actually distributed their electrons into the orbitals.

Periodic Properties
One of the really cool things about electron configurations is their relationship to the periodic table. Basically the periodic table was constructed so that
elements with similar electron configurations would be aligned into the same groups (columns).

Periodic Table showing last orbital filled for each element

The periodic table shown above demonstrates how the configuration of each element was aligned so that the last orbital filled is the same except for the
shell. The reason this was done is that the configuration of an element gives the element its properties and similar configurations yield similar properties.

Let's go through some of the Periodic Properties that are influenced directly by the electron configuration:

Atomic Size

The size of
atoms
increases
going down
in the
periodic
table. This
should be
intuitive
since with
each row of
the table you
are adding a
shell (n).

What is not
as intuitive is
why the size
decreases
from left to
right. But
again the
construction
of the
electron
configuration
gives us the
answer.
What are
you doing as
you go across
the periodic
table?
Answer,
adding
protons to
the nucleus
and adding
electrons to
the valence
shell of the
element.
What is not
changing as
you cross a
period?
Answer, the
inner shell
electrons.

So think of it
this way, the
inner shell
electrons are
a shield
against the
pull of the
nucleus. As
you cross a
period and
increase the
number of
protons in
the nucleus
you increase
its pull but
since you are
only adding
electrons to
the new shell
the shield is
not
increasing
but remains
the same all
the way
across. This
means the
pull on the
electrons
being added
to the
valence shell
is increasing
steadily all
the way
across. What
happens if
you pull
harder on
the
electrons?
Well, they
come closer
to the
nucleus and
the size of
the atom
 decreases.
The effect of
the nucleus
pulling on
the electrons
being added
across a
period is
called the
effective
nuclear
charge and is
calculated as
ZEff =
#protons -
Core #
Electrons.

So for
example the
pull felt by
Sulfur would
be ZEff = 16 -
10 = +6

Electronegativity

Electronegativity may be the most important of the periodic properties you can learn and understand since so many other properties are depend on its
value. Electronegativity is an atoms ability to pull electrons towards itself.

Electronegativity is generally expressed by the Pauling Scale and the values were determined experimentally. The table below shows the scale values for
the elements.
The electronegativity values increase from left to right and bottom to top in the periodic table excluding the Noble gases. The most electronegative
element is Fluorine.

From these electronegativity values we can derive the patterns of two other periodic properties: Ionization Energy and Electron Affinity.

Ionization Energy

Ionization energy is the amount of

energy required to remove an
electron from an atom. All
ionization energies are positive
values because all of these removals
(even those for elements that form
positive ions) require input of energy.
The more electronegative the
element, the higher the ionization
eneregy.

Electron Affinity

The Electron Affinity of an element is the amount of energy gained or Image result for
released with the addition of an electron. The electronegativity and Electron electron affinity
Affinity increases in the same pattern in the periodic table. Left to right and
bottom to top.