2P32 – Principles in Inorganic Chemistry Dr. M.

Pilkington

Lecture 17 – Periodicity and “The Network”

1. Electron affinity
2. Electronegativity
3. Summary of general trends in the network
4. Uniqueness principle
5. Diagonal effect

1.Electron Affinity
Energy change when an electron is added to a neutral atom in the gas phase.
M(g) + e- M-(g)

As you go down the group it

is more difficult to add an
electron as the Zeff is
reduced since the electron
to be added is further away
from effective nuclear
charge.

Hence, less energy is given

out when the electron is
added.

Variations of the electron affinities (in KJmol-1) of the representative elements.

ƒ An element on the right hand side of the periodic table where Zeff is greater
should add an electron more easily than an atom on the left hand side.
ƒ As a consequence those on the right will release more energies and have larger
-ve values for their electron affinities e.g. Na -53 KJmol-1, Cl -348 KJmol-1

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Exceptions:
1. Li to Be: The first exception is explained by referring to the orbital diagrams
of 1A and 2A elements, Note that the incoming electron of a 2A element must
occupy an np orbital which is of higher energy than the ns orbital to be
occupied by the incoming electron of the 1A element.

Accordingly, less energy will be released in the case of a 2A element.

lA: incoming electron

ns npx npy npz

2A: incoming electron

ns npx npy npz

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2. C to N: The second exception is also explained by referring to a set
of appropriate orbital diagrams.
The incoming electron of a 4A element occupies the remaining empty
np orbital, while for a 5A element, the new electron must be put in an
np orbital already occupied.
In the latter, electron-electron repulsions make the incoming electron
more difficult to add (and less energy is released) than expected
based solely on trends in effective nuclear charge.

4A: ns incoming electron

npx npy npz

5A: incoming electron

ns npx npy npz

2. Electronegativity - The ability of an atom in a molecule to attract electrons

to itself.

Electronegativity increases across a period due to increasing effective nuclear charge i.e. the
atomic number increases and as a consequence the pull or desire for electrons increases.

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 Electronegativity decreases down a group due to increasing atomic size

3. To summarize and emphasize the importance of network ideas, the general

trends are shown below:

A summary of the general vertical and horizontal periodic trends in effective

nuclear charge (Zeff), atomic radii, ionization energies (IE), electron affinities (EA),
and electronegativities (EN).
There are other organizing ideas apart from the more familiar periodic law:

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4. Uniqueness Principle

ƒ The chemistry of the 2nd row elements (Li, Be, B, C, N, O, F, Ne) are
significantly different from the chemistry of subsequent rows.

H He
Li Be B C N O F Ne These elements are different
Na Mg Al Si P S Cl Ar than the other elements in their
families

ƒ Why is the second row element different from others in its group?
ƒ Exceptionally small size of 2nd period elements.
ƒ Second row elements have no d-orbitals, for example:
N 1s2, 2s2, 2p3……. next orbitals are in 3s
P 1s2, 2s2, 2p3, 3s2, 3p3 ……. next orbitals are 3d.
ƒ Remember - the availability of d-orbitals in heavier members of each group
make expanded octets possible.
ƒ Second row elements form strong π-bonds (3rd and higher rows do not).

O
For Example: CH3CCH3 (CH3)2CO acetone
C vs. Si (CH3)2SiO silicone

Silicone forms a polymer

CH3 CH3 CH3

Si O Si O Si siloxanes

CH3 CH3
CH3

but
H H
C2H4 C C

H H

Si2H4 does not exist

Conclusion: we cannot predict the effects of Si based on C

Li Be B C N O F
Na Mg Al Si P S Cl

most pronounced differences are between the second and third row

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 CO2 vs SiO2
molecular network structure
gas with each Si bonded to
4 O’s.

http://cst-www.nrl.navy.mil/lattice/struk.jmol/c10.html

O O

R-C-R' R-Si-R' does not exist as this molecule

Ketones it polymerises to silicone rubber

Consequences of smaller size – the first elements are exceptionally small in comparison with
their congeners.

„ LiCl, RLi have significant covalent character (soluble in organic solvents) in comparison with
NaCl and RNa+.
„ This is due to the polarizing ability of small cations. Polarizing ability is the capacity of a
cation to distort the electron cloud of an adjacent atom. Take LiCl for example:

Li+ Cl- Li+ Cl-

Cl- is polarizable- soft

Electronegativity of Cl-
becomes distorted as Li+
pulls Cl- electrons towards
itself.

„ Low IE for Li and high exothermic electron affinity for Cl could be more correctly thought
of as Li+ Cl- BUT the small Li+ cation can get very close to the filled electron cloud of the Cl-
anion, so close that the diffuse Cl electron cloud is distorted or polarized by the Li+.
„ This makes orbital overlap between the two ions more likely and is characteristic of a
covalent bond.

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„ There is an increased likelihood of π-bonding in the first elements.
„ The small size of the second row elements increases the chances of π-bond
formation between themselves or other elements.
„ π-bonds are weaker in the third period than the second (why see later).

π-bond strengths vs σ-bond strengths

C=C 256 KJmol-1 346 KJmol-1
Si=Si 120 KJmol-1 222 KJmol-1
N=N 387 KJmol-1 167 KJmol-1
P=P 140 KJmol-1 201 KJmol-1
O=O 352 KJmol-1 142 KJmol-1
S=S 199 KJmol-1 226 KJmol-1

„ This has important consequences in chemistry for example consider the high
π-bond strength of N=N.

Gunpowder contains NH4NO3

NH4NO3 is intrinsically unstable
NH4NO3 N2 + 2H2O + 1/2O2
The driving force for the reaction is the stability of the N2 molecule.

Ammonium nitrate was first synthesized by

Johann R.Glauber in 1659 when he
combined ammonium carbonate and nitric
acid, but the ultimate power of the
explosive was not discovered until the end
of World War I.

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Explosives – a historical perspective.

„ The quest for a bigger and better explosives has led to many famous and

important scientific discoveries, one of which being ammonium nitrate.

„ It all began with the development of saltpeter, a nitrogenous ingredient found by

alchemists to be explosive when added to other ingredients.

„ This led to the creation of gun powder by the Chinese which was later used in

guns, cannons, and fireworks.

„ In order to create a faster reaction, scientists developed high explosives by

mixing nitrogen, carbon, oxygen, and hydrogen atoms at the atomic scale.

„ Nitroglycerine is just one of the first high explosives and its high sensitivity was

tamed by Alfred Nobel when he created dynamite.

Fritz Haber won the Nobel Prize in 1918

for forming the ammonia synthesis process.

„ Dynamite is still used, but has now been replaced widely by ammonium nitrate.
Fritz Haber won the Nobel Prize in 1918 for forming the ammonia synthesis
process.
„ Throughout the war, ammonia synthesis plants were built and used in Germany to
supply the country with explosives. The plants were able to form ammonia by
using the Haber-Bosch process.
„ Carl Bosch won the Nobel Prize in 1931 for industrializing and discovering a
catalyst for Haber's process. developed by Nobel Prize winner, Fritz Haber and
later industrialized by Nobel Prize winner, Carl Bosch. The process combined
hydrogen and nitrogen under extreme high pressure to form ammonia.

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„ At the end of the war, a large surplus of ammonium nitrate was left when the
first ammonia synthesis plant was closed down.
„ A huge pile of the compound was stored in an open field; in attempts to break
apart the pile for removal, explosives were drilled into holes in the pile. Contrary
to what was expected, the whole mound detonated with a blast of 4,500 tons,
killing 600 people.
„ There have been two other famous incidents where ammonium nitrate was the
source of great destruction: Texas city and Oklahoma city.

The ammonium nitrate explosion of Texas city

Oklahoma City Bombing

The Murrah Building after the terrorist bombing.

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Elemental nitrogen

„ Elemental N2 is shown below, elemental phosphorus is P4 or polymorphic with P-P

single bonds.

N2(g) :N N: P4 P

P:
allows for strong p-bonding P: P:
and it can readily form N2
tetrahedral P4
P2 does not exist because the π-bonds in exists in spite of bond strain
this case are weaker than the σ because of the weaker π-bond
compared to the σ-bond

2 P P less stable than P4

2 N N more stable than N4

„ Why does the π-bonding decrease when going from 2nd row to 3rd row
elements?

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5. The Elements of the Diagonal Effect

Li Mg
Be Al
B Si

A diagonal relationship exists between the chemistry of the 1st member of a group and that of the
second member of the next group. These pairs of compounds have much chemistry in common:

1. Atomic radii – the similar atomic radii which are found on the diagonal allows the elements to be
interchangeable. (Be and Al are fairly interchangeable in various crystal lattices.

2. Electronegativity - elements with similar electronegativities will form bonds of similar nature.
(Be and Al have an electroneg of 1.5, so they will polarize an M-X bond to the same extent).

3. Charge density – they are similar. It allows elements diagonally related to polarize with the
same abilities. Charge density accounts for variations in the size of the element as well as its
charge. Elements with high charge densities form covalent bonds to allow for a reduction in their
charge, For example, C has a high charge density and forms covalent bonds.

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