CHEM1011 / 1031

Mastery Practice Problem.

Topic 2: Atomic Structure

• Straightforward question from Mastery lecture

• Single concept
• Taught in lectures.

Question 1

The fourth row of the periodic table is reproduced below.

a) Complete the shorthand electron configurations for the following atoms. The first is
done for you as an example:
Atom Electron configuration
Ge [Ar] 4s2 3d10 4p2
Ca [Ar] 4s2
Ti [Ar] 4s2 3d2
Cr [Ar] 4s1 3d5
Mn [Ar] 4s2 3d5
Cu [Ar] 4s1 3d10
Br [Ar] 4s2 3d10 4p5

b) Complete the electron configurations for the following ions.

Ion Electron configuration

As+ [Ar] 4s2 3d10 4p2
Ca2+ [Ar]
Ti2+ [Ar] 4s0 3d2
Cu+ [Ar] 4s0 3d10
Cu2+ [Ar] 4s0 3d9
Br– [Ar] 4s2 3d10 4p6 = [Kr]
K– [Ar] 4s2
Cr– [Ar] 4s2 3d5
Question 2
a) Explain why, in general, there is a decrease in atomic radius from left to right across the
second row of the periodic table (lithium to neon), but an abrupt increase in radius on
going to the next row.

b) Explain the trends in electron affinities for the first 5 elements of the second row of the
periodic table, in terms of their electronic configurations, i.e. Discuss the trend in ΔH for the
following reaction: A(g) + e– → A–(g)

Element Li Be B C N
Electron affinity –60 0 –27 –122 0
(kJ mol–1)
Question 3

The first ionization energies of neon, sodium and magnesium are 2080, 494 and 736 kJ/mol
respectively.

a) Explain why the first ionization energy of magnesium is higher than sodium.

Na and Mg both have valence electrons in the 3s orbital. These electrons are well-shielded
from the nuclear charge by the complete (core) n = 2 set of orbitals.. Electrons in the same
valence shell do not provide as effective shielding because their average radius is similar. The
higher effective nuclear charge of Mg will attract the 2s electrons more strongly than Na,
thereby lowering their energy. As a consequence, it takes more energy to pull an electron off
Mg than Na, hence higher first IE.

b) Explain why the first ionization energy of neon is higher than sodium.

The Ne valence electrons are 2s, 2p and experience shielding mostly from the 1s orbital. The
effective nuclear charge for Ne valence electrons is therefore very high and the Ne electrons are
held very tightly. As a consequence the energy to remove an electron is very high causing a
very high IE.

(Note that this also gives rise to a smaller atomic size, so this question could have been pitched
as atomic size instead of IE)).

c) Write a (chemical) equation to represent the process when the second ionization of Mg
is measured from the Mg atom.

Mg + energy → Mg+ + e- (first ionisation energy)

Mg+ + energy → Mg2+ + e- (second ionisation energy)

d) Which of the three atoms do you predict will have the highest second ionization energy?
Explain your reason(s).

The electron configurations of the three singly charged ions are:

Mg+ : 1s2 2s2 2p6 3s1. Na+ : 1s2 2s2 2p6 Ne+ : 1s2 2s2 2p5
Mg+ still has a 3s electron that is on its own in the valence shell. Although it experiences is
higher nuclear charge than Mg neutral, it is still shielded by the n=2 core and is relatively easy
to remove (for a second IE).

Na+ has the same electron configuration as Ne, but with one extra positive charge in the nucleus
compared to Ne. So it would be held more tightly than Ne. Removing an electron is removing
from an ideal gas (filled shell) configuration and will have a very high second IE

Ne+ has an electron configuration the same as F, again with one more positive charge than F.
So both Ne+ and Na+ should have much higher second IEs than first IEs. Na+ should be
highest, because it has a higher effective nuclear charge than Ne+.

The actual 2nd IEs are: Mg: 1451, Na: 4562, Ne: 3952 kJ/mol

Question 4

The graph below shows the first ionisation energies (IEs), in blue, and second ionization
energies, in black, for second row elements of the periodic table.

a) Explain the general increase in first IE from atomic number 3 to 10.

Increasing effective nuclear charge holds the electrons of the same shell more tightly.

b) What is the maximum number of electrons that can be accommodated in an s orbital?

What evidence is there in the figure to support your answer?
Two electrons can occupy an s orbital. The slight decrease from element 4 to 5 is caused by
filling the s orbital with 2 electrons, and then third valence electron goes into a p orbital, which
experiences different shielding because of its different shape.

c) What evidence supports the fact that the 2p orbital lies at higher energy than the 2s?
Remember “higher energy” means less tightly held. The decrease in IE from element 4 to 5
means that the highest energy occupied orbital of element 5 (a p orbital) is higher than the
highest occupied orbital of element 4. Indeed, based solely on effective nuclear charge, you
might expect element 5 to have a higher IE, but it is in fact lower because the p orbital lies at
higher energy.
 d) Explain the anomalous behaviour from number 4 to 5 and 7 to 8.
The anomalous behaviour from 4 to 5 is explained above.
The IE decreases from 7 to 8 because in element 7, the three electrons in p orbitals can occupy
three different p orbitals (px, py, pz) to minimise electron-electron repulsion. For element 8, two
of the electrons must pair up in a p orbital. This increased electron-electron repulsion makes it
easier to remove an electron and therefore element 8 has a lower IE than expected.

e) Explain why the second ionization energy is higher than the first in every case.
Increased effective nuclear charge holds the remaining electrons more tightly, causing a higher
second IE.

f) Why is the second IE of atomic number 3 so high (in fact it is >7000 kJ/mol!)
The electron configuration of element 3+ is the same as element 2 (He) which is a noble gas
configuration. Nobel gases have the highest IEs of any element in their row. The higher
effective nuclear charge of element 3 cation (Li+) makes the IE even higher than the neutral
nobel gas (He)

g) Why have the anomalies shifted by one atomic number for the second IEs?
Because the electron configuration have shifted to that of one element earlier in the table. For
example, the cation of element 9 has the same electron configuration as element 8. The
anomalies are related to the electron configuration, not the atomic number (which is on the x-
axis of the figure). All the reasons for the anomalies described above for the neutral elements
remains the same for the same electron configuration, but shifted up by one in atomic number.

Question 5

Consider the types of molecular orbitals that can be formed from constructive and destructive
inference of two atomic orbitals. In the table below, consider two atomic orbitals interacting in
the prescribed configuration and complete the table. The first row is done for you as an
example.

Orbital: Atom 1 Orbital: Atom 2 Molecule bonding Molecule, anti-bonding

and name and name orbital and name orbital and name

s orbital s orbital s orbital s* orbital

Name: p orbital Name: p orbital Name: p orbital Name: p* orbital

 Name: p orbital Name: s orbital
s orbital Name: s* orbital

Name: s orbital
Name: p orbital Name: p orbital Name: s* orbital

Question 6

• Unfamiliar question topic (not taught in lectures)

• Requires knowledge from outside the course (a bit of
geometry)
• Requires critical thinking because the approach is not
described in the question.

Silicon and tin have the same structure as diamond. Use the information in the following table
to predict the density of tin.

Element Atomic Mass Density (g cm–3) Bond length (pm)

Si 28 2.329 233
Sn 118 280
Question 7

• Unfamiliar question topic (not taught in lectures)

• Likely not seen this molecule before
• Requires critical thinking because the approach is not
described in the question.
• Requires explanation that is not in lectures.

a) In lecture M2, we examined the bonding in the primordial molecule HeH+. Another
unusual molecule is the cation, He2+. Repeat the process in the lecture for He2+ and
determine what orbitals the three electrons in He2+ will occupy.

Configuration: 1s2 1s*2

b) Do you predict that He2+ will have a stable bond? Why?

I would predict that He2+ would have a stable bond It has 2 electrons in bonding orbitals
and 1 in an anti-bonding orbital. It therefore has an excess of bonding character and a bond
order, b = ½ according to MO theory (refer to Lecture M3).

c) Do you think the bond will be stronger, weaker or similar strength to HeH+? Why?

HeH+ has a bond order, b = 1. So I would predict a weaker bond for He2+