Week 3/4

CHEM1000 Principles and Processes in Chemistry

Workshop 3 Activity 2.2: Atomic Orbitals

Activity 2.2: Atomic orbitals

As we discovered in Activity 2.1, the simple Bohr model of the atom does not hold for elements from boron
onwards. We introduced the concept of a subshell to account for variations in ionisation energies
discovered by photoelectron spectroscopy. The new model for the atom proposes a series of subshells.
These subshells are given new symbols related to their spectroscopic properties - we call these labels
spectroscopic symbols.
Each electron within an atom now resides in an atomic orbital, which can be partially described by the
spectroscopic symbol and fully described by a series of four quantum numbers. The shape and distribution
of electrons within these atomic orbitals is important in describing how atoms share electrons to form
molecules, and it will be necessary for us to conceptualise these when we continue our journey through
Modules 3 and 4.
The electron configurations that we can now describe can also help us to understand why many properties
of atoms have a repeating pattern (periodicity) when plotted on a graph. The similarities are due to the
repeating pattern of electron configurations involving atomic orbitals. These empirically observed periodic
trends provide further evidence for the shell and subshell structure of atoms and the meaningful
arrangement of elements in the periodic table.

Learning Objectives

Describe the distribution of electrons within atomic orbitals.

Identify an electron within an atomic orbital by a series of quantum numbers.

Develop relationships between electron configurations, position in the periodic table and ionisation
energy.

Resources
Blackman, Bottle, Schmid, Mocerino & Wille, Chemistry, Chapter 4.54.7, pp 122138.

Model 1a: Quantum numbers

Table 1 Quantum numbers used to fully describe an electron within an atomic orbital

Symbol

Quantum
number

Description

Characterises

Allowed Values

Principal

Shell

Size and energy of atomic

orbital

n = 1, 2, 3, ... ,

= 0, 1, 2, ... , n 1
Shape, energy and number of
angular nodes in an atomic
spectroscopic symbols
orbital
s: = 0, p: = 1, d: = 2 f: = 3

Azimuthal

Subshell

Magnetic

Orientation

Orientation of an
atomic orbital

2 + 1 values of m
m = , + 1, ..., 0, ..., 1,

ms

Spin

Electron spin

Electron spin

+ or

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Critical Thinking Questions

1.

What are the possible values of:

a)

, when n = 2?

b)

m, when = 2?

c)

m when n = 3 and = 1?

2.

What is the minimum value of n possible for a d atomic orbital?

3.

If an f atomic orbital has an azimuthal quantum number, = 3, what are the possible values of m, and
how many f atomic orbitals would be found for a single value of n?

4.

Explain briefly why the following atomic orbitals can never exist:
a)

1p (n = 1, = 1)

b)

2d (n = 2, = 2)

c)

2f (n = 2, = 3)

5.

If a single atomic orbital can be described by (n, , m) and an electron within this orbital can be
described by (n, , m, ms), how many electrons can reside within a single atomic orbital?
Hint: in a single atom no two electrons can have the same series of quantum numbers1.

6.

Based on your answers to CTQs 35, how many electrons in total can each of the following subshells
hold?

7.

a)

s ( = 0)

b)

p ( = 1)

c)

d ( = 2)

d)

f ( = 3)

How many electrons can exist in the following shells?

a)

n=1

b)

n=2

c)

n=3

d)

n=4

This is called the Pauli exclusion principle.

Activity 2.2: Atomic orbitals

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Model 1b: Boundary surfaces

A boundary surface is the three dimensional area within which an electron assigned to an atomic orbital
will spend 90-95% of its time. Chemists use these boundary surfaces to describe the regions of maximum
electron density for a particular atomic orbital.
Table 2: Boundary surfaces for s, p and d atomic orbitals.
(Atkins et al, Shriver & Atkins: Inorganic Chemistry, 4th ed, Figure 1.15 - 1.18)

Activity 2.2: Atomic orbitals

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Critical Thinking Questions

8.

Which quantum number (n, , m, ms) describes the characteristic shape of an atomic orbital?

9.

Which quantum number (n, , m, ms) describes the orientation of an atomic orbital of any given
shape?

10.

For each subshell value of = 0, 1 and 2, what are the possible values of m and what are the labels for
atomic orbitals with these and m values?

possible m values

orbital labels as per Model 1

0
1
2

11.

Which orbitals in the model have a plane that includes the origin where the probability of finding an
electron is zero? The origin is where the axes cross. These planes are called angular nodal planes and a
node is the place where a wave has zero amplitude. In Model 1 these are shown as green surfaces.

12.

Which quantum number (n, , m) tells us the number of angular nodes? Explain your reasoning

Activity 2.2: Atomic orbitals

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Model 2: Ionisation energies

Table 4: Ionisation energies (MJ mol1) for the first 18 elements
Element

1s

2s

2p

3s

Table 5: Electron configurations for

selected elements
3p

Element

Configuration

1.31

1s1

He

2.37

He

1s2

Li

6.56

0.52

Be

1s2 2s2

Be

11.5

0.9

1s2 2s2 2p2

19.3

1.36

0.8

Ne

1s2 2s2 2p6

28.6

1.72

1.09

Mg

1s2 2s2 2p6 3s2

39.6

2.45

1.4

52.6

3.04

1.31

67.2

3.88

1.68

Ne

84

4.68

2.08

Na

104

6.84

3.67

0.5

Mg

126

9.07

5.31

0.74

Al

151

12.1

7.19

1.09

0.58

Si

178

15.1

10.3

1.46

0.79

208

18.7

13.5

1.95

1.06

239

22.7

16.5

2.05

Cl

273

26.8

20.2

2.44

1.25

Ar

309

31.5

24.1

2.82

1.52

Critical Thinking Questions

13.

What is the first (lowest) energy ionisation (Ei1) energy of:

a)

N?

b)

Ar?

14.

For CTQ13, write the subshell that the electrons lost in the first ionisation are removed from.

15.

Describe what information is provided by electron configuration as it is shown in Table 5?

Activity 2.2: Atomic orbitals

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16.

17.

What do you notice about the general trend in ionisation energies for the following atomic orbitals:
a)

1s

b)

2s

c)

2p

Identify any anomalies in this general trend, i.e. a localised change between two values that goes
against the trend.

Activity 2.2: Atomic orbitals

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Model 3: Simulated photoelectron spectrum of potassium

347

37.1

3.93

29.1

2.38

0.42

Decreasing Ionisation energy (MJ mol1)

Indicates a discontinuity in the scale

Table 6: Ionisation energies (MJ mol1) for selected elements

Element

1s

2s

2p

3s

3p

3d

347

37.1

29.1

3.93

2.38

0.42

Ca

390

42.7

34

4.65

2.9

0.59

Sc

433

48.5

39.2

5.44

3.24

0.77

4s

0.63

Critical Thinking Questions

18.

Assign the peaks for the PES spectrum shown in Model 3 to the subshells represented in Table 6, and
also write the number of electrons in each of these subshells by considering the comparative heights of
each peak.

19.

Based on your answer to CTQ 18, write the electron configuration for K.

20.

Write the electron configurations for:

a)

Ca

b)

Sc

21.

Suggest a reason for why the 4s subshell fills before the 3d.

22.

In the photoelectron spectrum of Sc the peak at 0.63 MJ mol1 is allocated to the 4s subshell and the
peak at 0.77 MJ mol1 is allocated to the 3d subshell. Suggest why the 3d subshell fills before the 4p
subshells.

23.

The majority of elements from Sc to Zn have stable 2+ cations after loss of two electrons from the 4s
orbital, leaving 3d electrons only as the valence subshell which is why these elements are often called
the d block. What other elements might also belong to the d block?

Activity 2.2: Atomic orbitals

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Model 4: The Periodic Table

Note that the periodic table has an unusual form, given here in the elongated arrangement with the
lanthanoids and actinoids in. Columns are called groups (18 in the main table), rows are called
periods and a collection of columns is called a block.
1
H

18
2

13 14 15 16 17

Li Be

d block

Mg

K Ca

He
Ne

9 10 11 12
Ga

Lanthanoids
Actinoids

Critical Thinking Questions

24.

For each of the elements, except scandium, examined in Models 2 and 3 write the subshell with the
lowest ionisation energy in each elements position on the periodic table.

25.

What is the relationship between the form of the periodic table and the electron configurations of the
elements?

26.

Based on the form of the periodic table above, how many electrons is the 3d subshell capable of
holding?

27.

Predict the electron configuration of Ga.

28.

What is the common feature of electron configurations for elements of the same group?

29.

As atomic orbitals are filled in the aufbau3 process, predict which orbital will fill immediately after the
6s atomic orbital?

aufbau = German word for building.

Activity 2.2: Atomic orbitals

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Model 5: Electron spin

Each atomic orbital can hold two electrons, each with
a unique value of magnetic spin quantum number ms
of .
When the value is positive the electron is represented
by an upward arrow and is said to be spin up. If the
value is negative the electron is represented by a
downward arrow and is said to be spin down.
Each electron can act like a magnet and can be
influenced by surrounding magnetic fields. If all
atomic orbitals have electrons fully paired up it is said
to be diamagnetic and the atom will have a magnetic
moment (s) of 0 and be repelled by a surrounding
magnetic field. If there are any unpaired electrons then
s > 0 and the atom will be attracted to a magnetic
field. These atoms are said to be paramagnetic.

Table 7: Magnetic moments for several elements.

Element

Magnetism

Paramagnetic

1.7

He

Diamagnetic

Paramagnetic

1.7

Paramagnetic

2.8

Paramagnetic

3.9

Paramagnetic

2.8

Ne

Diamagnetic

Critical Thinking Questions / Homework Problems

30.

Based on the data in Table 7 rank the following atoms in terms of the number of unpaired electrons in
each atom: B, C, N, O, Ne. Explain your reasoning clearly.

31.

Make an electron energy diagram for carbon similar to those in Activity 2.1, Model 54 that shows why it
is paramagnetic. Explain how your diagram is consistent with your answer to CTQ30 and the data in
Table 7.

32.

Repeat CTQ33 for N and again for O. Based on your answers to CTQs 34 and 35, is pairing of
electrons in an atomic orbital an attractive or a repulsive process?

See Chapter 4.7 of Blackman et al, Chemistry for more guidance on electron energy level diagrams.

Activity 2.2: Atomic orbitals

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Homework Problems
1.

2.

3.

For the following spectroscopic symbols determine which describe actual atomic orbitals and which
are nonexistent. For those that are nonexistent list the restriction(s) that forbid it.
a)

2d

b)

2f

c)

6g

d)

6i

For the following sets of quantum numbers (n, , m, ms), determine which describe actual atomic
orbitals and which are nonexistent. For those that are nonexistent list the restriction(s) that forbid it.
a)

(3, 1, 1, )

b)

(3, 1, 1, )

c)

(3, 1, 2, )

d)

(3, 2, 2, )

Complete the following table.

n

Spectroscopic
notation(s)

Total number of
electrons

0
2

+2, +1, 0, 1, 2
5f

4.

Sketch the boundary surfaces of the 4py, 4dx2y2 and 4dxy atomic orbitals. Clearly mark any angular
nodes and label all axes. How many radial nodes will each orbital have?

5.

Place the following in order of increasing energy to remove an electron from a 1s atomic orbital:
C, Pt, Ba, Ne, Zn, Gd.

6.

Make a rough sketch of the photoelectron spectrum of vanadium. Indicate the subshell that gives rise
to each peak and its relative height.

7.

Give the electron configurations for:

a)

P and P3

b)

Ba and Ba2+

c)

S and S2

d)

Ni and Zn

8.

Consider your answers to CTQs 21 and 35. Give an explanation for the localised anomaly in the
ionisation energy between N and O or P and S as a result of their subshell electron configurations.

9.

The 3d subshell can hold ten electrons. Make an electron energy diagram for Ni similar to CTQ34 and
predict its magnetic properties.

Activity 2.2: Atomic orbitals

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