Interactions between atoms – the formation of chemical bonds

Chemistry would be very boring if atoms sat around doing nothing - in fact, if that
were the case, there wouldn't be anything called chemistry (or anything alive for
that matter) since chemistry is, at its essence, the science of how atoms interact
with each other. If these interactions are large enough, then atoms will stick
together strongly enough that we must consider them as a single unit. For example,
under normal ambient conditions, oxygen does not exist as the naked atom, it
actually exists as a dimer known as the dioxygen molecule (O2). The fundamental
reason why we don't see individual atoms of oxygen floating around is that they are
more stable when connected to other atoms... the formation of the dioxygen
molecule is energetically favourable. In fact, if we look at the formation of O2 from
its atoms, we find that ~500kJ/mol of energy is released when the molecule is
formed.
2O  O2 + 498 kJ / mol
This means that it is significantly more beneficial for oxygen to exist as dioxygen
than to stay as individual atoms. But how are these two atoms connected to each
other? What happens to the atoms to release so much energy? The answer is that
the electrons in each of the atoms are rearranging themselves in response to the
presence of the other atom. Basically, the electronic structure of the molecule is
different from the electronic structure of atoms. In doing so, the atoms form what
we call a chemical bond - a connection between the two atoms that holds them
together. As we have seen previously, it is the valence electrons that are closest to
the 'surface' of an atom, so it should not be surprising that the electrons involved in
the formation of these chemical bonds. But what exactly happens when chemical
bonds are formed?
There are two fundamental ways that two atoms can come together to form a
chemical bond - and thus form a diatomic molecule. The difference between these
two approaches to chemical bonding ultimately depends on how different the two
partners are. In the example above, the two partners are oxygen and they are
identical to each other. This is one extreme case and this is a case that will yield
chemical bonds known as covalent bonds. Another extreme case would be the
reaction of Cs with Cl - a reaction that we have seen previously when discussing the
reactivity of the s-block elements. In that case, the two elements are about as
different as one could imagine. How do they compare when considering the
periodic trends that we have explored? When these elements come together, they
will form bonds that are known as ionic bonds. Let's consider ionic bonding first and
then turn our attention to covalent bonding.

Ionic bonding
We have seen that chlorine actually exists as a dimer (Cl2) under normal
circumstances but let us ignore that for the moment and consider the reaction of a
Cs atom with Cl atom. We have already seen that Cs very easily loses one electron
to form the Cs+ monocation; this results from Cs having a very low ionization energy
(I1 = 376 kJ/mol). At the same time, based on the position of Cl in the periodic table,
we know that Cl has a very large electron affinity (EA = -349 kJ/mol). We therefore
have a situation where one partner is looking to get rid of a valence electron
whereas the other is looking to receive one. The reaction, known as an electron
transfer reaction, causes the formation of the Cs+ and Cl- ions as shown in the first
step below.
1
 Cs(g) + Cl(g)  Cs + (g) + Cl-(g)  electron transfer 
Cs + (g) + Cl-(g)  Cs Cl 
+ -
(g)
ion pair formation 
If we focus simply on that first step, we see that very little energy is required to
form the gas phase ions. How much energy is required to get the first step to occur?
Importantly, we have now created two ions that are oppositely charged! These will
come together through electrostatic attraction to form what we call an ion pair (a
pair of ions connected to each other). This ion pair is held together by an ionic bond
- an electrostatic attraction that occurs because the two partners are oppositely
charged. The strength of this interaction can be quite easily estimated by using the
following equation for the electrostatic potential energy:
Q1Q2
Ek where k 1.389 107 m   kJ / mol 
r
The values of Q1 and Q2 are the charge of the two ions (+1 and -1, respectively), r
is the distance between the two ions in the ion pair, and k is Coulomb's constant.
For example, if we take the ion pair distance for {Cs+Cl-}(g) as the sum of the two
component ionic radii (1.69 Å + 1.81Å = 3.50Å), we obtain an estimated energy for
the formation of the ion pair of about -400 kJ/mol, which more than compensates
for the slight endothermicity of the initial electron transfer reaction.
From the above, we see that there are two main issues that we need to worry
about when considering the formation of ionic bonds. The first part is the energy
needed to form the ions in the first place. In all cases, the ionization energy is larger
than the electron affinity, which implies that there is always a price to pay in
creating the ions. However, in the case of CsCl, the price is very small compared to
payoff! Calculate the overall energy released on going from the gas phase atoms to
the ion pair and you'll see how big the overall benefit is for the formation of a gas
phase CsCl ion pair.
After all of that, we need to realise that having CsCl in the gas phase is not a
"normal" situation. Under typical ambient conditions, CsCl is a solid and it is quite
different from the simple ion pair that we've discussed up until now. When forming
a solid from the Cs+ and Cl- ions, the ions will arrange themselves so that each of the
ions maximizes its interaction with the oppositely charged ions as a way of
stabilizing the compound as much as possible. We will see in Lab #7 that different
ionic compounds arrange themselves in different three-dimensional structures,
depending on what is best for them. The formation of the three-dimensional lattice
is much more stable than just the simple ion pair. The lattice energy is the energy
that is gained by creating the three-dimensional lattice and it makes for very stable
ionic structures.
Let us now look at a different situation, where the formation of ionic bonds isn't
as favourable. Let's now look at bringing two Cl atoms together to form Cl2. We can
generate the same kind of chemical reaction equation as we did for CsCl, forming
the cation and anion through electron transfer and then formation of the ion pair as
follows:
Cl(g) + Cl(g)  Cl+ (g) + Cl-(g)  electron transfer 
Cl+ (g) + Cl-(g)  Cl Cl 
+ -
(g)
ion pair formation 
To calculate the energetics of the first process, we need to know I and EA for the
Cl atom: I = 1251 kJ/mol and EA = -349 kJ/mol. From this, we find that the
2
formation of the component ions will require approximately 900 kJ/mol! This is a lot
of energy, but maybe the formation of the ion pair will compensate... Using a Cl-Cl
distance of 2.30Å (0.49 Å + 1.81Å), we calculate that the second step will provide us
with only about 600 kJ/mol of energy, which clearly isn't enough to compensate for
the 900 kJ/mol required in the first step. Clearly, the formation of an ionic bond
between a Cl+ and a Cl- ion cannot account for the formation of the Cl2 molecule
since we're 300 kJ/mol short of breaking even! Something else must be happening...
and that something is the formation of a covalent bond.

Covalent bonding
Experimentally, it is known that the Cl-Cl bond requires ~250 kJ/mol to break so
we can't explain this by invoking simple electrostatic interactions (as we just saw).
In situations where you don't have one atom that clearly wants an electron (high
EA) and another that wants to get rid of one (small I), there is no benefit in doing a
complete electron transfer from one atom to another. However, there is a chance
that each atom might benefit from sharing valence electrons. The act of sharing
electrons between two or more atoms is known as covalent bonding.
As a general rule, atoms have a tendency to prefer having an electronic
configuration that is similar to their nearest noble gas. We have already seen this
in the s-block elements although we haven't discussed it in this way. Each of the
alkali metals has a single valence electron. If we remove that valence electron, the
cation will have the same electronic configuration as the previous element (a noble
gas!). For example, sodium has 11 electrons which are divided as follows: 2
electrons in the n = 1 shell, 8 electrons in n = 2, and 1 valence electron in n = 3. By
removing one electron, we find that Na+ has 2 electrons in n = 1 and 8 electrons in n
= 2. This is exactly the same electronic configuration as the noble gas known as
neon (Ne). In the same way, each of the alkali metal cations are electronically
isoelectronic to one of the noble gases. Furthermore, each of the alkaline earth
dications are also isoelectronic with the noble gases.
Using this information, we can create a correlation table of isoelectronic species
as shown below. All of the species listed has the electronic configuration of a noble
gas - and this turns out to be a good thing. Although this is true, it sometimes
requires too much energy to achieve these configurations by complete electron
transfer. As we have just seen, in order for the Cl atom to achieve the same
configuration as Ar, it must gain an electron - but it can't completely take an
electron from another Cl atom because that would create a Cl+ cation, which costs
too much energy.

Be2+  Li +  He
Mg 2+  Na +  Ne  F-  O 2-
Ca 2+  K+  Ar  Cl-  S2-
Sr 2+  Rb +  Kr  Br -  Se 2-
Ba 2+  Cs +  Xe  I-  Te 2-
The act of sharing electrons, however, allows atoms to achieve their desired
electronic configuration without having to go through the expense of transferring
electrons completely. What if both Cl atom could achieve a configuration similar to
Ar - wouldn't that be best? The answer is a definite yes - but how do they do that?

3
 Let's go back to our Cl2 example. Initially, each Cl atom has 7 valence electrons and
they each wish to gain one (to have 8) and have the same configuration as Ar. If
they share a pair of electrons such that those electrons spend time on both atoms,
each of those atoms will think that it has 8 electrons in its valence shell. By sharing
one pair of electrons, each Cl atom will have achieved the electronic configuration
of Ar without too much of a penalty. We can represent this situation as shown in
Figure 1. In this situation, each of the Cl atoms still owns 6 valence electrons
outright and a pair of electrons is shared between them. This sharing of electrons
allows each atom to achieve its desired electronic configuration and stabilizes the
system. The sharing of electrons also means that these atoms cannot get too far
away from one another - otherwise they would miss out on the shared electrons.
Figure 1. Two chlorine atoms come
The shared pair of electrons is therefore responsible for the chemical bond that together to form a covalent bond. The
now connects the two atoms. shoring of a pair of electrons allows
each atom to have access to 8 valence
electrons.
Summary
There are two limiting cases for bonding in molecules. In a situation where the
complete transfer of electrons is energetically feasible, the formation of ionic bonds
occurs. However, in cases where the formation of ions is very difficult, atoms will
share electrons in order to achieve a more stable state. The description of covalent
bonding using Lewis Theory is the next topic up for discussion.