Faculty of Science

Molecular Sciences

Academic year 2023-2024

Bachelor 1

Structure of Atoms and Molecules

Study Guide

Dr. René de Gelder

Nature, 498, 9 (2013); Phys. Rev. Lett., 110, 213001 (2013):

Direct view of atomic orbitals

Electron orbitals of excited hydrogen atoms can be observed directly

Orbitals lie outside the nucleus and their properties are
described by mathematical wave functions. These functions
are difficult to study because measuring observable
components can destroy other quantum features.
Aneta Stodolna at the FOM Institute for Atomic and
Molecular Physics in Amsterdam, Marc Vrakking at the Max
Born Institute in Berlin and their colleagues designed a
quantum microscope to study hydrogen orbitals directly.
Their system used tunable lasers to excite electrons in a
hydrogen atom placed in an electric field. An electrostatic
lens then stretched and magnified the orbitals — without
disturbing the internal structure — until individual electrons
hit a detector. After recording about 50,000 electrons, the
team produced images to show the structure of the electron
orbital (pictured) of atoms at different excited states.

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 Page

CONTENTS 3

INTRODUCTION 5

PROGRAMME ACADEMIC YEAR 2023-2024 10

COURSE MATERIAL, EXCERCISES AND OBJECTIVES

Part 1
Required reading 11
Testing exercises 11
Objectives 11
Exercises for part 1 12
Part 2
Required reading 14
Testing exercises 14
Objectives 14
Exercises for part 2 15
Part 3
Required reading 17
Testing exercises 17
Objectives 17
Exercises for part 3 18
Part 4
Required reading 20
Testing exercises 20
Objectives 20
Exercises for part 4 21

SOLUTIONS TO THE EXERCISES

Part 1 23
Part 2 29
Part 3 36
Part 4 50

INFORMATION ACCOMPANYING THE COMPUTER MODULE 58

APPENDICES
1.1 General information and physical constants 61
1.2 The atom through the ages 61
1.3 A few important formulas 61
1.4 Converting from eV to J; energy as a wavenumber 62
1.5 The difference between the functions R(r), R(r)2 and r2R(r)2 63
1.6 The number of nodes in wave functions 63
1.7 The relation between the quantum numbers 63
2.1 The Periodic Table of the Elements 64
2.2 Electron configuration of atoms compared to ions 64
2.3 Trends in radii and ionisation energy 65
2.4 Strategy for the construction of Lewis structures 66
2.5 Definition of formal charge 66
2.6 Definition of formal oxidation state 66
2.7 Validity of the octet rule 66
2.8 Electronic structure and molecular geometry 67
3.1 Strategy for the construction of an MO diagram 68
3.2 Estimation of a few atomic orbital energies 69
4.1 Crystal Field Stabilisation Energy for an octahedral complex 70
4.2 Octahedral complexes: low spin or high spin? 70
4.3 Tetrahedral and square planar complexes 70
4.4 Total electron count metal (donor-pair method) 71
4.5 Intermolecular interactions 71

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4
INTRODUCTION

Course outline

In the course “Structure of Atoms and Molecules” a first insight is given in the way chemical
bonds in molecules can be described. The question what quantum mechanics can teach us,
in a qualitative way, about the electronic structure of atoms will be considered in depth. This
knowledge can then be applied to better understand and predict the bonds between atoms in
molecules. Several approaches to describe the geometry and electronic structure of molecules
will be discussed. In addition, the interactions between molecules will be covered.
The study load of this course is 3.0 ECTS and the following teaching formats are used:
lectures, tutor sessions, tutorial sessions, computer sessions and self-study, which includes
(among others) reading the books and self-study assignments.

Why Structure of Atoms and Molecules?

To become a good writer or poet one needs to learn the alphabet and the meaning of words,
but one should also have insight into the origin of the language and the rules of grammar. In
addition, the ability to judge the strength and coherence between words and sentences needs
to be developed.
A molecular scientist doesn’t just require knowledge of the elements in the periodic table. The
scientist needs to be aware of the fact that creating and changing molecules, by breaking
bonds and by forming new ones, is bound to specific rules. These rules originate from the
electronic structure of the elements and the way these elements share electrons. How does
one synthesize a substance from nature? Why is a certain type of bond that reactive?
The spatial structure of a molecule, which is determined by the rules of chemical bonding,
determines for a large part its chemical and physical properties. How does an enzyme work?
What is the underlying mechanism behind a successful medicine?
The world around us does not just consist of separate molecules, rather, these molecules
exhibit coherence and structure together. The meaning of a chemical bond therefore reaches
further than just the description of a bond between individual atoms. Why doesn’t a human
body directly fall apart? Why is ice less dense than water?
Proper insight into the principles of bonding, the consequences of such a chemical bond for
the structure of molecules, and the forces between molecules, is needed to become a
molecular scientist. This course will contribute to this insight.
The knowledge and skills that will be acquired during this course are not just useful on their
own. Other courses will rely on and build upon the foundation first laid in this course. The
course “Structure of Atoms and Molecules” is therefore the first one in a series of coherent
courses spanning the entirety of your study.

Objective

After successfully completing this course, you will be able to qualitatively describe the bonds
between atoms on the basis of a quantum mechanical approach of the electronic structure of
atoms and molecules. You are able to use practical models, both simple and advanced, for the
prediction and explanation of chemical bonds and molecular structure. In addition, you can
indicate all interactions that can possibly exist between molecules.

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For whom is this course intended?

The course “Structure of Atoms and Molecules” is intended for first-year students of the
Molecular Sciences cluster (Chemistry, Molecular Life Sciences and Science).

Study Load

As stated earlier, the study load for this course is 3.0 ECTS, at least for regular students of the
Molecular Sciences cluster. 45 hours are scheduled and are divided as follows:

- Lectures: 14 hours
- Tutorials: 14 hours
- Computer sessions “Molecular Bonding”: 3 hours
- Tutor sessions: 6 hours
- Self-study assignments: 6 hours
- Exam: 2 hours (2.5 hours for extra time students)

Prior knowledge

This course builds upon the “Scheikunde” (Chemistry) and “Natuurkunde” (Physics) classes of
the VWO (pre-university secondary education). Certain students might come from different
countries, or may have studied at an HBO (University of Applied Sciences). Because of these
different backgrounds, there will be differences between the theoretical knowledge you might
possess. This course aims to level these differences and to ensure the same final qualifications
for all students. This requires effort on the teacher’s side, but must be accompanied by active
student participation. It takes two to tango…

During the course there will be help from so called “tutors” who will facilitate the transition from
your prior education to university education. Always inform either the teacher or the tutors
when problems regarding your prior knowledge arise.
Because this course tries to lay a foundation for different courses during your studies, special
attention has been paid to realize a proper transition between the courses. A result is that
several books are shared among courses. We hope that this coherence will be really
experienced during your studies.

The exam and allowed resources

The course “Structure of Atoms and Molecules” will be concluded by means of a written exam
on Friday the 3rd of November 2023 from 12.45 to 14.45.

Please note:
During the exam you are not allowed to use the study guide, books or graphical calculators
(such as the Casio fx-9860GII(SD) or fx-CG50, Texas Instruments TI-84 or TI-Nspire CX,
Hewlett Packard HP Prime etcetera). You are allowed to use a regular calculator.
Appendices 1.1, 2.1 and 3.2 from this study guide will also be provided as an appendix with
the exam.

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Course period

The course “Structure of Atoms and Molecules” will be given from the 6th of September 2023
until the 19th of October 2023.

Teacher

The teacher’s information is: Dr. R. (René) de Gelder

Solid State Chemistry
Institute for Molecules and Materials
Room HG03.629 (Huygens building)
Phone: 024-3652842
E-mail: [email protected]

Tutors

Drs. E. (Els) Heijmen e-mail: [email protected]

Ir. A. (Ade) Hoekstra e-mail: [email protected]
V. (Vicky) E.M. Mertens MSc e-mail: [email protected]
Drs. A. (André) Steenbergen e-mail: [email protected]
Ir. M. (Martin) Waals e-mail: [email protected]

Literature and course materials

Weller, Overton, Rourke, Armstrong: Inorganic Chemistry, Seventh Edition, Oxford University
Press, 2018, ISBN 978-0-19-876812-8. Will be abbreviated as: IC

Alen Hadzovic: Solutions Manual to Accompany Inorganic Chemistry, Seventh Edition, Oxford
University Press, 2018, ISBN 978-0-19-881468-9.

Please note: The "Solutions Manual" by Hadzovic contains answers to exercises at the end
of the chapters in the Inorganic Chemistry book by Weller et al.

Paula Y. Bruice: Organic Chemistry, Eighth Global Edition, Pearson Education, 2017, ISBN
978-1-292-16034-4. Will be abbreviated as: OC

Paula Y. Bruice: Study Guide and Student’s Solutions Manual for Organic Chemistry, Eighth
Global Edition, Pearson Education, 2017, ISBN 978-1-292-16043-6.

Study Guide "Structure of Atoms and Molecules", 2023-2024, by René de Gelder.

Available in Brightspace.

Please note: The books “Inorganic Chemistry” (IC) and “Organic Chemistry” (OC) will also be
used in other courses during the bachelor program.

Please note: The “Inorganic Chemistry” (IC) book and “Study Guide” should be brought to
each tutor session and tutorial session!

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Digital Learning Environment

Information about the course can be found on: brightspace.ru.nl

The Study Guide

This study guide is meant to be a guide throughout the “Structure of Atoms and Molecules”
course, and aims to aid the student in successfully completing the exam. This study guide is
intentionally not meant to be used as lecture notes. During the course two books, and
accompanying solution manuals, will be used. The study guide merely serves as a guide and
tool when studying these books: it provides an overview of which material is relevant to the
course and the exam (“Required reading”), and offers an extensive series of exercises
(“Testing exercises”). In addition, it provides the student with clear study goals (“Objectives”).

The material can roughly be separated into the following four parts:

Part 1 - What is Inorganic and Organic Chemistry?

- What is an atom according to a chemist?
Part 2 - Why is the Periodic Table periodic?
- Simple models for the description of the bond between atoms
Part 3 - Better models for the description of the bond between atoms
- Bonds between poly-atomic molecules
Part 4 - Binding and reactivity of d-block elements
- Interactions between molecules

For each part, the study guide indicates what material from the books should be studied
(“Required reading), which exercises should be made (“Testing exercises”) and what you are
expected to know and be able to during the exam (“Objectives”). This will aid you in staying on
schedule regarding studying the material and making the exercises.

The study guide contains a variety of exercises with solutions for each part.

In addition, the study guide provides information about the computer sessions and several
useful appendices.

Self-study and how to use the study guide

In determining this course’s study load it was assumed that self-study would make up a
significant part of the course. The course is structured in such a way that the exam can be
completed with good results if you participate in all scheduled activities and take sufficient time
to study by yourself.
Self-study allows you to once again go through the material, which has already been covered
in the lectures and tutorials, by reading the books. In addition the course material is
supplemented and delved deeper into by the books. The teacher will try to cover the most
important subjects during the lectures, but he will not cover all material in full detail. An
important part of academic education is the ability to be self-sufficient in covering new theory,
but you will of course be provided with lots of help during your studies.
In addition, the self-study time can be used to do the exercises for each part of the study guide.
This way, you will stay on schedule and you will have had plenty of exercise near the end of
the course.

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The exam questions for the course “Structure of Atoms and Molecules” are a reflection of the
exercises presented in this study guide. Making the exercises in a serious manner will therefore
increase your chances of succeeding in this course.
Every week there are two hours of lecture. The self-study assignments will closely follow the
material covered in the lectures. This self-study assignment will be discussed in the
subsequent tutor session, where you can also ask questions about subjects other than the
self-study assignment.
The other self-study time can be scheduled by yourself. You may do this either alone, or with
other students. It is strongly recommended to use the study guide as a guideline. By following
the schedule and looking at the overview of to-be-covered exercises and material you can
make sure not to fall behind. It is in any case important to read all paragraphs regarding this
week’s matter, and to make the accompanying exercises, in case you didn’t already finish them
during the tutorials. It is also advised that you read the material from the books that will be
covered in the upcoming lecture, in advance. As such, you will be way better prepared.
The reading of scientific English is often harder than people think. English in educational texts
often contains many technical terms, which causes the text to quickly become compact and
with a higher level of abstraction than you might be used to. Reading these texts therefore
requires both time and concentration.
To determine whether or not you have fully grasped a certain part you can make the
supplemental exercises that are indicated in the study guide. You can also test your knowledge
by studying the goals that are mentioned for each part in the study guide. Making lists of the
unclear things might greatly help you. If any subject matter remains unclear, you can ask the
tutors or teacher to help you.

Acknowledgement

When this study guide was first composed, among others, the lecture notes of the “Inleiding
Structuur” course, the precursor of this course, by dr. Willemse were used. Most notably the
exercises in this study guide, along with the accompanying solutions, were taken from these
lecture notes.
The tutors monitored, and still monitor, the theory covered in this course and its connection to
the expected prior knowledge. The feedback of the tutors during the course has continuously
helped improving the various course components.
Hens Borkent and Gijs Schaftenaar have greatly contributed by setting up, and improving
according to feedback, the computer modules that are used during this course. By visualizing
the orbitals and making interactive exercises on Lewis structures and MO diagrams the student
can improve the knowledge about these different subjects, and test this knowledge using the
computer whenever the student wants.

René de Gelder, September 2023

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PROGRAMME "Structure of Atoms and Molecules" Year 2023-2024

Week 1 Q1
Required reading: IC 1, 1.1 and 1.2; OC 1 and 1.1
Lecture: on campus (CC 2); see content section SAM in Brightspace for lecture slides
Self-study assignment: see content section SAM in Brightspace
Tutor/tutorial session: on campus, see schedule of the faculty
Exercises: 1.1. up to and including 1.8 (Study Guide SAM)

Week 2 Q1
Required reading: IC 1.3, 1.4, 1.5, 1.6 and 1.7; OC 1.5
Lecture: on campus (CC 2); see content section SAM in Brightspace for lecture slides
Self-study assignment: see content section SAM in Brightspace
Tutor/tutorial session: on campus, see schedule of the faculty
Exercises: 1.9 up to and including 1.14; 2.1 and 2.2 (Study Guide SAM)

Week 3 Q1
Required reading: IC 2, 2.1, 2.2, 2.3, 2.11, 2.12, 2.13, 9.1, 9.2 and 9.5; OC 1.2, 1.3 and 1.4
Lecture: on campus (CC 2); see content section SAM in Brightspace for lecture slides
Self-study assignment: see content section SAM in Brightspace
Tutor/tutorial session: on campus, see schedule of the faculty
Computer session: on campus, see content section SAM in Brightspace
Exercises: 2.3 up to and including 2.15 (Study Guide SAM)

Week 4 Q1
Required reading: IC 2.4, 2.5, 2.6, 2.7 and 2.8; OC 1.6
Lecture: on campus (CC 2); see content section SAM in Brightspace for lecture slides
Self-study assignment: see content section SAM in Brightspace
Tutor/tutorial session: on campus, see schedule of the faculty
Exercises: 3.1 up to and including 3.7 (Study Guide SAM)

Week 5 Q1
Required reading: IC 2.9 and 2.10; OC 1.7, 1.8, 1.9, 1.10, 1.11, 1.12, 1.13, 1.14 and 1.15
Lecture: on campus (CC 2); see content section SAM in Brightspace for lecture slides
Self-study assignment: see content section SAM in Brightspace
Tutor/tutorial session: on campus, see schedule of the faculty
Exercises: 3.8 up to and including 3.13 (Study Guide SAM)

Week 6 Q1
Required reading: IC 3.6, 3.7, 3.11, 19.2, 20.1, 3.3 and 10.6; OC 1.16
Appendix 4.5 of the Study Guide (Intermolecular interactions)
Lecture: on campus (CC 2); see content section SAM in Brightspace for lecture slides
Self-study assignment: see content section SAM in Brightspace
Tutor/tutorial session: on campus, see schedule of the faculty
Exercises: 3.14 up to and including 3.18; 4.10 up to and including 4.15 (Study Guide SAM)

Week 7 Q1
Required reading: IC 22.3, 22.21, 22.22, 22.24, 22.25 and 25.4
Lecture: on campus (CC 2); see content section SAM in Brightspace for lecture slides
Self-study assignment: see content section SAM in Brightspace
Tutor/tutorial session: on campus, see schedule of the faculty
Computer session: on campus, see content section SAM in Brightspace
Exercises: 4.1 up to and including 4.9 (Study Guide SAM)

Week 9 Q1
Friday 3 November: 12.45 - 14.45 Exam SAM

Week 5 Q2
Wednesday 6 December: 15.30 - 17.15 Remedial teaching

Week 6 Q2
Wednesday 13 December: 15.30 - 17.15 Remedial teaching

Week 7 Q2
Wednesday 20 December: 15.30 - 17.15 Remedial teaching

Week 10 Q2
Thursday 25 January: 12.45 - 14.45 Resit SAM

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COURSE MATERIAL, EXERCISES AND OBJECTIVES

PART 1

Required reading

IC 1 The structures of hydrogenic atoms

IC 1.1 Spectroscopic information
IC 1.2 Some principles of quantum mechanics
IC 1.3 Atomic Orbitals
IC 1.4 Many-electron atoms: Penetration and shielding

OC 1 Introduction
OC 1.1 The structure of an atom
OC 1.5 Atomic orbitals

Testing exercises

Exercises belonging to Part 1 in this study guide, found on page 12 and onwards.

Supplementary exercises from the books:

IC: exercises 1.1 to 1.18

OC: exercises in the sections mentioned

Objectives

After part 1:

- You know an atom consists of neutrons, protons and electrons.

- You know the difference between the atomic number and atomic mass.
- You know the relation between the wavelength, the wavenumber and the frequency of
photons.
- You can determine the wavelength corresponding to a certain photon frequency and
vice versa.
- You know the relation between the wavelength, the frequency and the energy of
photons.
- You can determine the wavelength that corresponds to a certain photon energy and
vice versa.
- You can determine the wavelength that corresponds to a particle with a given mass
and speed.
- You can perform calculations with moles and Avogadro’s number.
- You can clarify an atomic spectrum based on quantum numbers and Rydberg’s formula
(even for Z>1, see Appendix 1.3).
- You can relate the ionisation energy to energy levels.
- You can explain what the effective nuclear charge and its relation to shielding is.
- You can explain the Bohr-model (in a qualitative way).
- You know when quantization of energy occurs.
- You know what Heisenberg’s uncertainty principle is.
- You know the rules concerning the quantum numbers: the coherence between the
principal quantum number n, the orbital angular momentum quantum number l, the
magnetic quantum number ml and the spin magnetic quantum number ms.

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 - You know the relation between the quantum numbers and the shape and orientation of
the orbitals.
- You know the spatial orientation and shape of the different s, p and d-orbitals.
- You know the relative position of the energy levels of orbitals in atoms with multiple
electrons.
- You know what is meant by: wave-particle duality, wave function, quantum number,
orbital, normalization, probability density, radial distribution function, node, degeneracy,
ground state, shielding and penetration of orbitals.

Exercises for Part 1

EXERCISE 1.1
The bright yellow light emitted by a sodium vapour lamp consists of two emission lines at 589.0 nm and
589.6 nm. What are the frequency and the energy of a photon of light at each of these wavelengths?

EXERCISE 1.2
An ancient but consistent set of units that may be used in the de Broglie equation (see Appendix 1.3) is
 in cm, mass in g, velocity in cm s-1. h (Planck's constant) is, using these units: 6.63∙10-27 g cm2 s-1.
What is the wavelength in cm and in Å of:
(a) an electron traveling at 106 cm s-1, a velocity typical in the electron microscope?
(b) a ball with a mass of 2.00∙102 grams, thrown at 103 cm s-1?
Show that 6.63∙10-27 g cm2 s-1 is equal to 6.63∙10-34 J s.

EXERCISE 1.3
Calculate the energy per photon and the energy per mole of photons for radiation of wavelength:
(a) 700 nm (red), (b) 400 nm (violet), (c) 150 pm (X-ray).
Calculate the linear momenta of the photons specified.

EXERCISE 1.4
The bond energy of the Cl-Cl bond in the Cl2 molecule is 2.43∙105 J mol-1 .
What is the wavelength in nm and colour of light needed to break the Cl-Cl bond?

EXERCISE 1.5
The 'Humphries series' is another group of lines in the spectrum of atomic hydrogen (see page 7 IC and
Appendix 1.3). It begins at 12368 nm and has been traced to 3281.4 nm.
Calculate the value of n1 in the Humphries series.
What are the wavelengths of the first five transitions?

EXERCISE 1.6
The Li2+ ion is hydrogenic (hydrogen-like) and has a series that starts at 740747 cm-1, 877924 cm-1,
925933 cm-1, and beyond. Show that the energy levels are of the form K(1-1/n2). What is the name of
this series? Find the value of K for this ion.
Go on to predict the two longest-wavelength transitions of the Balmer series of the ion and find the
ionization energy of the ion.

EXERCISE 1.7
A particle of mass 6.65∙10-27 kg is confined to an infinite square well of width L. The energy of the level
to which n = 3 is 2.00∙10-24 J. Calculate the width of the box using the formula given in Appendix 1.3.

EXERCISE 1.8
Calculate the energy difference between the levels with n = 4 and n = 5 of a deuterium atom in a one-
dimensional box of length 5.0 nm (see Appendix 1.3).

EXERCISE 1.9
The first ionization energy for Li is 517.5 kJ mol-1. This corresponds to complete removal of the electron
from the nucleus, and is achieved when n = .
Calculate from this the effective nuclear charge felt by the 2s electron of Li by assuming that the atom
is hydrogen-like. Why is this less than the actual nuclear charge of +3?

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EXERCISE 1.10
Which of the following are possible sets of quantum numbers for an electron?
For the sets of quantum numbers that are not possible, state what is wrong with each set.

a) n = 1, l = 0, ml = 1, ms = +½ b) n = 9, l = 7, ml = -6, ms = -½
c) n = 2, l = 1, ml = 0, ms = 0 d) n = 1, l = 1, ml = 1, ms = +½
e) n = 3, l = 2, ml = -3, ms = +½ f) n = 4, l = 0, ml = 0, ms = -½

EXERCISE 1.11
What is the maximum number of orbitals for n = 5? And for n = 4, l = 2?
EXERCISE 1.12
Compare the energy (in eV) of a single electron in a 3px orbital for H and Li2+.
EXERCISE 1.13
How many levels in hydrogen have energy: (a) -hcR, (b) -hcR/9, and (c) -hcR/25?
EXERCISE 1.14
How many electrons can occupy the following orbitals: (a) 1s (b) 3p (c) 3d (d) 6f ?

Hints accompanying Part 1

linear momentum = mv
angular momentum = mvr
nm = nanometer = 10-9 m
pm = picometer = 10-12 m
Å = 10-10 m
J = CV = kg m2 s-2
mole = 6.02214∙1023 particles

Significant numbers

Significant numbers are reliable values for measurements and calculations. During your former
education you have probably learned that measurements and calculations should be rounded
off in such a way that every number must have a meaning. After multiplication or division the
answer should have just as many significant numbers as the least significant value you used
in the calculation. After addition or subtraction, the answer should have just as many decimal
values as the value with the smallest number of decimals you used for your calculation.
In the answers and elaboration to the exercises in this study guide, rounding off is not always
consequently done according to these rules. As such, it may sometimes occur that your
carefully obtained answers slightly differ from the answers you may find in this study guide.

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PART 2

Required reading

IC 1.5 The building-up principle

IC 1.6 The classification of the elements
IC 1.7 Atomic properties
IC 2 Lewis structures
IC 2.1 The octet rule
IC 2.2 Resonance
IC 2.3 The VSEPR model
IC 2.11 Bond length
IC 2.12 Bond strength
IC 2.13 Electronegativity and bond enthalpy
IC 9.1 Valence electron configurations
IC 9.2 Atomic parameters
IC 9.5 Oxidation states

OC 1.2 How the electrons in an atom are distributed

OC 1.3 Covalent bonds
OC 1.4 How the structure of a compound is represented

Testing exercises

Exercises belonging to Part 2 in this study guide, found on page 15 and onwards.

Supplementary exercises from the books:

IC: exercises 1.19 to 1.30, 2.1 to 2.8, 2.16, 2.17, 9.8, 10.2 and 10.6
OC: exercises in the sections mentioned, as well as: 49, 50, 53, 54, 55, 57, 58, 61,
63, 66, 70, 72 and 77 from Chapter 1.

Objectives

After part 2:

- You know the Pauli exclusion principle.

- You know Hund’s rule.
- You can apply the Aufbau (building-up) principle.
- You can tell the electron configuration of atoms and ions by using the atomic number
and/or the Periodic table.
- You can differentiate between “valence” and “core” electrons.
- You can explain trends in the Periodic Table based on electron configurations.
- You know the terms ionization energy, electron affinity, and electronegativity.
- You know which role spin-pairing energy plays in filling orbitals.
- You know what is meant by para and diamagnetism.
- You know what is meant by: ionic model, covalent model, resonance, lone pair.
- You can construct Lewis structures of molecules and ions.
- You can apply the octet rule.
- You can determine the formal charge of an atom.
- You can determine the formal oxidation state (oxidation number) of an atom.
- You can draw resonance structures and indicate their “weight”.

14
 - You can use the VSEPR method to predict the geometry of small molecules.
- You know the names of the various basic shapes and molecular shapes (up to and
including six electron regions).
- You know how the angles of the basic shapes (and thus the molecular shapes) can be
modified by differences in electrostatic repulsion.

Exercises for Part 2

EXERCISE 2.1
What is the ground-state electronic configuration of the atoms with the atomic numbers 7, 20, 26, 32?

EXERCISE 2.2
Give the electronic configurations of P, Mn, Te2-, Cr2+, Co2+, Mo4+, Ir3+, Cu2+ and Cu+ (see Appendix 2.2).

EXERCISE 2.3
Arrange the following groups of atoms in order of increasing size and first ionization energy (see
Appendix 2.3):

a) Be, Mg, Ca b) Te, I, Xe c) Ga, Ge, In d) As, N, F e) S, Cl, F

EXERCISE 2.4
Why is the first ionization energy of the oxygen atom lower than that of the nitrogen atom?

EXERCISE 2.5
Explain the trend in ionization energies for the noble gases.

EXERCISE 2.6
For each of the following sets write down the atoms in the order of increasing first ionization energies.
Give arguments for your choice.

a) Be, N, F b) Be, Ca, Ba c) Be, B, C

d) N, O, F e) F, Cl, Br f) Si, P, S

EXERCISE 2.7
Which atom in the following pairs has the highest IE1? Al or Mg; Zn or Ca? Explain why.

EXERCISE 2.8
In a sodium atom the valence electron has been promoted to an excited 4s state. Is this excited
electron easier or harder to remove than the valence electron in potassium? Explain!

EXERCISE 2.9
Show that there are several possible Lewis structures (see Appendix 2.4) for the chlorate anion, ClO3-.
Indicate the formal charges of the atoms (see Appendix 2.5).
Point out where the octet rule (see Appendix 2.7) isn’t fulfilled and give a brief justification.
Predict the geometry based on VSEPR theory.

EXERCISE 2.10
Predict, using the VSEPR theory, the structure of H2NOH (hydroxylamine), BaCl2, XeO2F2, (CH3)2SeO,
and (H2N)2CO (urea).
Indicate for all compounds whether the angles are more obtuse, more acute, or equal to that of the ideal
basic arrangement.
Indicate, where applicable, the most important resonance structures.
Explain all answers.

15
EXERCISE 2.11
Write down the electronic structural formulas for each of the following molecules. Your formulas should
include formal charges, if any, and reasonable resonance structures.
Mention the geometrical arrangement of the atoms around the central atoms.

a) SO42- b) CH3COO- c) ClF3 d) SF4 e) HNO3 f) PO43-

EXERCISE 2.12
Which of the following structures (connectivities) of N2F4 found below is the most stable one? Explain
your answer using Lewis structures.

(Note that the dashes indicate bonds, although these need not necessarily be single bonds.)

Apart from NF3, PF3 and PF5, NF5 also exists. What is the electronic structure of this last compound?
What is its geometry?

EXERCISE 2.13
Which of the following triatomic molecules and ions are expected to be linear:

(a) CO2 (b) NO2+ (c) NO2- (d) SO2 (e) H2O (f) H2O2+

EXERCISE 2.14
Draw the three most important resonance structures for cyanogen azide, CN4, given that the atoms
are bonded in the order NNNCN. Indicate all valence electrons and formal charges.
Can you predict whether the molecule will be bent or linear?

EXERCISE 2.15
The structure of the pentafluorotellurate monoanion [TeF5]-1 has been determined by X-ray techniques.
What is the oxidation number of Te in this anion?
Draw the Lewis structure for the anion.
Determine the geometry and explain any deviations from ideal geometry.

Hints accompanying Part 2

IE1 = 1st ionization energy

16
PART 3

Required reading

IC 2.4 Valence bond theory: The hydrogen molecule

IC 2.5 Valence bond theory: Homonuclear diatomic molecules
IC 2.6 Valence bond theory: Polyatomic molecules
IC 2.7 Molecular orbital theory: An introduction to the theory
IC 2.8 Molecular orbital theory: Homonuclear diatomic molecules
IC 2.9 Molecular orbital theory: Heteronuclear diatomic molecules
IC 2.10 Molecular orbital theory: Bond properties
IC 3.6 The symmetries of molecular orbitals: Symmetry-adapted linear combinations
IC 3.7 The symmetries of molecular orbitals: The construction of molecular orbitals
IC 3.11 Representations: Polyatomic molecules

OC 1.6 An introduction to molecular orbital theory

OC 1.7 How single bonds are formed in organic compounds
OC 1.8 How a double bond is formed: the bonds in ethene
OC 1.9 How a triple bond is formed: the bonds in ethyne
OC 1.10 The bonds in the methyl cation, the methyl radical, and the methyl anion
OC 1.11 The bonds in ammonia and the ammonium ion
OC 1.12 The bonds in water
OC 1.13 The bond in a hydrogen halide
OC 1.14 Hybridization and molecular geometry
OC 1.15 Summary: hybridization, bond lengths, bond strengths, and bond angles

Testing exercises

Exercises belonging to Part 3 in this study guide, found on page 18 and onwards.

Supplementary exercises from the books:

IC: exercises 2.19 up to and including 2.28, 2.31 and 2.32

OC : exercises in the sections mentioned; as well as: 51, 52, 56, 60, 64, 65, 71, 73
and 75 from Chapter 1

Objectives

After part 3:

- You can name the interactions within molecules.

- You can explain the difference between VB and MO theory.
- You can apply VB theory to simple molecules.
- You can create an MO diagram for diatomic molecules if the orbital energies are given.
- You can indicate whether a bond is of the  or  type.
- You know how bonding, anti-bonding, and non-bonding combinations of AOs (the
resulting MOs) look with respect to their shape and spatial orientation.
- You know when you can apply sp, sp2 or sp3 hybridization.
- You can create an MO diagram using hybrids based on the geometry of molecules.
- You can create an MO diagram using Symmetry Adapted Linear Combinations of
atomic orbitals (SALCs).

17
 - You know the connection between bond strength and bondorder.
- You can determine the bondorder of a bond/molecule.
- You can reason, based on an MO diagram, whether a bond is covalent or polarized.
- You know what is meant by: LCAO, SALC, MO, overlap, orthogonal functions, bonding,
non-bonding, anti-bonding, bondorder, HOMO, LUMO, - crossover, iso-electronic,
hybridization, localized description, delocalized description, electron-deficient
compound.

Exercises for Part 3

EXERCISE 3.1
When a bond is formed between two atoms, they are drawn together. What limits their internuclear
distance so that they do not coalesce?

EXERCISE 3.2
In a compound A-B on both the A and B atom s and p-orbitals are available for the formation of
molecular orbitals. Choose a coordinate system (take the z-axis as the line between both nuclei) and
indicate which atomic orbitals, based on their symmetries, combine to give bonding molecular orbitals.
Indicate whether these combinations are of the  or  type.

EXERCISE 3.3
Which of the molecules N2, NO, O2, C2, F2 and CN would you expect to be stabilized by:
(a) the addition of an electron to form AB- (b) the removal of an electron to form AB+

EXERCISE 3.4
True or false: The set of valence shell orbitals (2s, 2p) for N are of higher energy than those for C.
Explain your answer.

EXERCISE 3.5
Sketch the molecular energy level diagram for XeF. The energy of Xe 5s is similar to F 2s and the
energy of Xe 5p is similar to F 2p. Neglect the overlap between s and p-orbitals. Is XeF likely to have a
shorter bond length than XeF+?

EXERCISE 3.6
What is the bondorder in Hg22+ and how does this change when the ion is reduced or oxidized?

EXERCISE 3.7
In a compound A-B the d-orbitals in A and the p-orbitals in B are available for the formation of
molecular orbitals. Choose a coordinate system (take the z-axis as the line between both nuclei) and
indicate which atomic orbitals, based on their symmetries, combine to give bonding molecular orbitals.
Indicate whether these combinations are of the  or  type.

EXERCISE 3.8
Give the ground state electronic configurations and bondorders of respectively C2, H2-, O2, NO and
CN-.
EXERCISE 3.9
From the ground state electronic configurations of B2 and C2 predict which molecule should have the
greater bond dissociation energy.

EXERCISE 3.10
Draw an MO diagram for the molecule LiF and discuss based on the diagram the bondorder and the
polarity.

EXERCISE 3.11
Describe the bond in H2O2 using hybrids and create a qualitative MO diagram.

18
EXERCISE 3.12
CO2, HgCl2 and (CN)2 are linear. Draw Lewis structures and assign hybridizations for each atom.

EXERCISE 3.13
Draw a qualitatively correct energy-level diagram for the CO2 molecule using only hybridization for the
carbon atom.
Show that it accounts correctly for the presence of double bonds.

EXERCISE 3.14
Give a description of NO2-
a) Using the possible Lewis structures.
b) Using an MO diagram. Use hybridization on all atoms.
Why do you need two MO diagrams to describe NO2- ?

EXERCISE 3.15
Give an MO diagram for CO32-, with a fully localized description and using hybridization on both C and
O and add the right number of electrons. Calculate the bondorder using the MO diagram.
What will be the MO diagram of CO32- when you describe the σ-skeleton and -system separately,
using hybrids for the σ-skeleton and SALCs for the -system?

EXERCISE 3.16
Draw Lewis structures for O3 (ozone) and SO2. For ozone,  OOO = 117o. For sulfur dioxide  OSO =
120o. Explain this difference in bond angles.
Formulate a molecular orbital description for the -skeleton of the ozone molecule using hybridization
for all oxygen atoms. Describe the -system separately using SALCs.

EXERCISE 3.17
The cyanate ion can be represented as CON-, CNO-, or OCN-.
Use Lewis structures to determine which of the formulas above describes the most stable compound.
Construct a localized MO diagram for this ion.

EXERCISE 3.18
Explain in detail, using both the MO approach and the resonance theory, why the NO bonds in NO3-
have a bondorder of 4/3. Give the MO diagram for one of the Lewis structures using hybrids only.

Hints accompanying Part 3

Bond dissociation energy = the energy needed to break a bond

MO = Molecular Orbital
Valence shell orbitals = Atomic Orbitals that (mostly) determine the bonding

19
PART 4

Required reading

IC 3.3 Polar molecules

IC 10.6 Compounds of hydrogen (iii) Hydrogen bonding
IC 19.2 The d-block elements: Chemical and physical properties
IC 20.1 Crystal field theory
IC 22.3 Electron counting and oxidation states: (b) Donor pair method
IC 22.21 Ligand substitution
IC 22.22 Oxidative addition and reductive elimination
IC 22.24 1,1 Migratory insertion reactions
IC 22.25 1,2-Insertions and β-hydride elimination
IC 25.4 Hydrogenation of alkenes

OC 1.16 Dipole moments of molecules

Appendix 4.5 of this study guide (Intermolecular interactions)

Testing exercises

Exercises belonging to Part 4 in this study guide, found on page 21 and onwards.

Supplementary exercises from the books:

IC: exercises 20.5, 20.6 and 20.24

OC: exercises in the sections mentioned, as well as: 62, 68, 74, 76 and 78 from
Chapter 1

Objectives

After Part 4

- You can determine the electron configuration of a transition metal in transition-metal

complexes.
- You can use Crystal Field Theory to explain colours and colour transitions in transition-
metal complexes.
- You know the Crystal Field splitting diagram for octahedral complexes.
- You globally know the spectrochemical series of ligands and metals.
- You know the limitations of the Crystal Field model.
- You know what is meant by: electrostatic, hydration, eg-set, t2g-set, o, weak field,
strong field, high spin, low spin and Crystal Field Stabilisation Energy.
- You can apply the donor-pair method to determine the oxidation number of a metal
atom and the total electron count (valence electrons) on the metal.
- You know what happens during a ligand association or a ligand dissociation reaction
on a d-block metal.
- You know what happens during a ligand substitution reaction on a d-block metal.
- You know what happens during an oxidative addition or a reductive elimination reaction
on a d-block metal.
- You know what happens during a migratory insertion or an α/β-elimination reaction on
a d-block metal.
- You know the effect of a d-block metal reaction on the total electron count, oxidation
number and coordination number of the metal.

20
 - You can explain a catalytic cycle involving a d-metal complex in terms of electron count,
coordination number, oxidation number and type of reactions on the metal.
- You can name and explain the various intermolecular forces.
- You know van der Waals interactions can be described using the Lennard-Jones
potential and you know the distance dependency of these forces.
- You know what is meant by: intermolecular forces, dipole moment, hydrogen bond,
polarizability and polarizability volume.

Exercises for Part 4

EXERCISE 4.1
By using orbital-splitting diagrams, show which dn electronic configurations are capable of giving either
low-spin or high-spin configurations in an octahedral crystal field.

EXERCISE 4.2
Calculate, in units of o, the CFSEs of the following high-spin ions in their octahedral complexes:

a) Fe2+ b) Mn2+ c) Mn3+ d) Co2+

EXERCISE 4.3
Predict the oxidation number of the central metal atom, the magnetic properties and the CFSE for
each of the following octahedral complexes:

(a) [Fe(CN)6]3- (b) [Ru(NH3)6]2+ (c) [Co(NH3)6]3+

(d) [PtCl6]2- (e) [Fe(H2O)6]2+ (f) [Mn(H2O)6]2+
(g) [CoF6]3- (h) [Cr(H2O)6]2+ (i) [Fe(CN)6]4-
(j) [Fe(H2O)6]3+ (k) [Cr(NH3)6]3+ (l) [Ru(NH3)6]3+

EXERCISE 4.4
Is the complex [Co(H2O)6]2+ para or diamagnetic?
Determine the oxidation state of the central atom, the total number of d-electrons and the number of
unpaired electrons.
Calculate the Crystal Field Stabilisation Energy for the complex.

EXERCISE 4.5
a) Argue using crystal field theory that [Co(CN)6]3- is much more stable than [Co(CN)6]4-.
b) The complex [Co(NH3)6]3+ is orange-yellow, [CoF6]3- is blue. Explain qualitatively the
difference.
c) How should the crystal field splitting diagram for [Co(NH3)6]3+ be changed to obtain the one for
[Co(NH3)5F]2+, taking into account the fact that NH3 and F- have different ligand strengths?
Note that the z-axis of the complex should go through the F atom.

EXERCISE 4.6
Predict the relative positions of the absorption maximum in the UV/Vis-spectra of:

a) [Ti(CN)6]3- b) [TiCl6]3- c) [Ti(H2O)6]3+

EXERCISE 4.7
A certain transition-metal ion forms two octahedral complexes from two different ligands, one whose
solution is red and the other blue.
Using simple crystal-field theory, explain which complex would be expected to arise from ligands that
create the stronger field.

21
EXERCISE 4.8
The ions [Mn(H2O)6]2+ and [Mn(CN)6]4- differ in colour and magnetic properties. Draw energy-level
diagrams illustrating the differences in crystal-field splitting of the d-orbitals for the two ions and the
distribution of electrons between the orbitals.
Why do the ions have different magnetic properties?
Which ion would you predict to absorb visible radiation of higher frequency?

EXERCISE 4.9
Wilkinson’s catalyst [RhCl(PPh3)3] is used for the
hydrogenation of alkenes. The catalytic cycle for the
hydrogenation of terminal alkenes is given in the
figure. Give for every compound A, B, C, D, E and F
the coordination number of the metal, the total
number of electrons in the valence shell of the metal
and the oxidation number of the metal. Give for
every step in the catalytic cycle the name of the
specific reaction type. How could you summarize
steps B-C-D?

EXERCISE 4.10
Which molecules from the following list should possess a permanent dipole moment?

a) CHCl3 b) SO42- c) 1,3,5-trinitrobenzene d) SO2 e) CO2 f) C2H2

EXERCISE 4.11
The ClF3 molecule is polar, which structure does it have?

EXERCISE 4.12
Methyl-2-hydroxybenzoate (methyl salicylate) and methyl-4-hydroxybenzoate both have the same
gross formula: HOC6H4COOCH3. The first compound has a melting point of -8oC, while the second
has a melting point of 127oC.
How can this large difference in melting points be explained?

EXERCISE 4.13
Formic acid, HCOOH, forms a dimer in the vapour phase.
Deduce a reasonable structure based on hydrogen bonds between the formic-acid molecules.

EXERCISE 4.14
Why are intermolecular attractions so strong in liquids and solids, but so weak in gases?

EXERCISE 4.15
What type(s) of intermolecular attractive forces are found in the following compounds?

a) HCl b) Ar c) CH4 d) HF
e) NO f) CO2 g) H2S h) SO2

Hints accompanying Part 4

CFSE = Crystal Field Stabilisation Energy
Visible radiation = visible light
Dimer = combination of two molecules
Vapour phase = gas phase

22
SOLUTIONS TO THE EXERCISES

Solutions to the exercises accompanying Part 1

EXERCISE 1.1
Exercise: The bright yellow light emitted by a sodium vapour lamp consist of two emission lines at
589.0 nm and 589.6 nm. What are the frequency and the energy of a photon of light at
each of these wavelengths?

Given:  of the two emission lines

Needed: , E.

Strategy: Determine the dimensions of ,  and E.

Find a formula that describes the relation between  and  and between  and E.

Solution:  = c/; E = h.

c = 2.9979∙108 ms-1; h = 6.6261∙10-34Js;

 = 589.0 nm  = 5.0898∙1014s-1 E = 3.3726∙10-19 J

 = 589.6 nm  = 5.0846∙1014s-1 E = 3.3691∙10-19 J

EXERCISE 1.2
Exercise: An ancient but consistent set of units that may be used in the de Broglie equation (see
Appendix 1.3) is  in cm, mass in g, velocity in cm s-1.
h (Planck's constant) is, using these units: 6.63∙10-27 g cm2 s-1.
What is the wavelength in cm and in Å of:
(a) an electron traveling at 106 cm s-1, a velocity typical in the electron microscope?
(b) a ball with a mass of 2.00∙102 grams, thrown at 103 cm s-1?
Show that 6.63∙10-27 g cm2 s-1 is equal to 6.63∙10-34 J s.

Given: a) Electron with v = 106 cm s-1. b) Ball with m = 2.00∙102 g and v = 103 cm s-1.

Needed: For a) and b)  in cm and in Å ( = 10-10 m).

Strategy: Find a formula that describes the relation between  and v (see Appendix 1.3).
Check whether this formula needs additional information, like the mass of an electron and
h, and look this up. Check the dimensions and convert these when needed.

N.B.: Beware of confusing the formulas E = ½mv2 and E = h.

For all particles:  = h/mv; for particles with v=c: E = h,  = c/, E = mc2.
For particles with v<c: E = ½mv2.

Solution:  = h/mv
me = 9.11∙10-31 kg = 9.11∙10-28 g.

a)  = (6.63∙10-27 g cm2 s-1)/(9.11∙10-28 g)(106 cm s-1) = 7.27∙10-6 cm = 727 Å.

b)  = (6.63∙10-27 g cm2 s-1)/(200 g)(103 cm s-1) = 3.31∙10-32 cm = 3.31∙10-24 Å.

Extra: h = 6.63∙10-34 J s (= kg m2 s-1) = 6.63∙10-34 (103 g) (104 cm2) s-1 = 6.63∙10-27 g cm2 s-1

23
EXERCISE 1.3
Exercise: Calculate the energy per photon and the energy per mole of photons for radiation of
wavelength: (a) 700 nm (red), (b) 400 nm (violet), (c) 150 pm (X-ray).
Calculate the linear momenta of the photons specified.
Given: Photons with specific .

Needed: a) Energy per photon.

b) Energy per mole of photons.
c) Linear momentum (p) of those photons.

Strategy: Find the formula that describes the relation between  and E.
Check the dimensions and calculate the answer to a).
Find the relation between a photon and a mole of photons; then convert this (b).
Find a relation between  and p, the linear momentum. Check the dimensions and convert
these when needed.

Solution: E = h = hc/; p = h/.

hc = (6.626∙10-34 J s) (2.9979∙108 m s-1) = 1.986∙10-25 J m;
hcNA = (1.986∙10-25 J m) (6.022∙1023 mol-1) = 0.1196 J m mol-1;
(nm) E(J) E(kJ mol-1) p(kg m s-1)
700 2.84∙10 -19 171 0.95∙10-27
400 4.97∙10 -19 299 1.66∙10-27
 = 150pm 1.32∙10 -15 7.98∙10 5 4.42∙10-24

EXERCISE 1.4
Exercise: The bond energy of the Cl-Cl bond in the Cl2 molecule is 2.43∙105 J mol-1.
What is the wavelength in nm and colour of light needed to break the Cl-Cl bond?

Given: Bond strength of 2.43∙105 J mol-1.

Needed:  and its corresponding colour.

Strategy: Find a formula that describes the relation between E and  for photons (see Appendix 1.3).

Solution: E = h = hc/ = 6.63∙10-34∙3∙108/ = 1.989∙10-25/ J s ∙ m s-1 ;

E = 2.43∙105 J mol-1 / 6.02214∙1023 mol-1 = 4.04∙10-19J   = 4.93∙10-7 m = 493 nm;
Colour: green-blue

EXERCISE 1.5
Exercise: The 'Humphries series' is another group of lines in the spectrum of atomic hydrogen (see
page 7 IC and Appendix 1.3). It begins at 12368 nm and has been traced to 3281.4 nm.
Calculate the value of n1 in the Humphries series.
What are the wavelengths of the first five transitions?

Given: (begin) and (end) of the Humphries series.

Needed: What is n1 and what is  for the transitions n(x+1)  n1 where x = 1, 2, 3, 4 and 5.

Strategy: A series, so: formula 1/ = Z2R(1/n12 – 1/n22) (See page 7 IC).
The calculation of n1 is important, for this the  for n2 =  is needed.
Determine which transition belongs to (end) (high energy = low ).
If n1 is known, the first five transitions can be calculated.

24
Solution: First the value of n1 for the Humphries series has to be determined; the following is valid:
Z = 1 and (1/) = Z2R{(1/n12) - (1/n22)}. For the last transition where ionization is possible,
the following is valid: n2 =  so (1/) = Z2R(1/n12)  n1 = 6. In the equation you can then fill
in for the first transition: n2 = n1 + 1 = 7  (1/) = R{(1/36) - (1/49}   = 12368∙10-9 m,
which is correct. The last transition is then the one that belongs to: n2 = .
The following transitions can then be calculated:
n2 = 8: 1/ = 1.33∙105   = 7498 nm
n2 = 9: 1/ = 1.69∙105   = 5905 nm
n2 = 10: 1/ = 1.95∙105   = 5126 nm
n2 = 11: 1/ = 2.14∙105   = 4670 nm

EXERCISE 1.6
Exercise: The Li2+ ion is hydrogenic (hydrogen-like) and has a series that starts at 740747 cm-1,
877924 cm-1, 925933 cm-1, and beyond.
Show that the energy levels are of the form K(1-1/n2). What is the name of this series? Find
the value of K for this ion.
Go on to predict the two longest-wavelength transitions of the Balmer series of the ion and
find the ionization energy of the ion.

Given: Li2+ has an electron configuration of 1s1 (because Li has configuration 1s22s1).
The series has dimension cm-1, so the numbers give: 1/ = Z2R(1/n12 – 1/n22). Z is not
needed, because we can explain the Z2R term with K.
Series with 1/ : 740747, 877924, 925933 and …. cm-1.

Needed: 1) Show that the energy levels follow: 1/ = K(1-1/n2) or better: K(1/n12 – 1/n22) with n1 = 1.
NB: 1/ is a measure for the energy levels, because E = hc/.
2) Lowest transitions (1/’s) for the Balmer series.
NB: Balmer means n1 = 2.
3) Ionization energy of Li2+.
NB: ionization: transition to n = .

Strategy: 1) The numbers from the series should be inserted in the formula: 1/ = K(1/n12 – 1/n22)
where n2 = subsequently 2, 3, 4; this yields K. If K consistently has the same value, the
energy levels satisfy the given formula.
2) With this K the transitions n1  n1 + 1 and n1  n1 + 2 for the Balmer series (n1 = 2)
can be calculated.
3) The ionisation of Li2+ can also be calculated by filling in n =  in the formula. While it isn’t
needed, it might be useful to calculate this energy in different dimensions.

Oplossing (1/) = K{(1/n12) - (1/n22)}; n1 = 1. Lyman series!

n2 = 2: (1/) = K{1 - (1/22)} = (3/4)K = 740747 cm-1  K = 987663 cm-1
n2 = 3: (8/9)K = 877924 cm-1  K = 987665 cm-1
n2 = 4: (15/16)K = 925933 cm-1  K = 987662 cm-1
n2 =  (1/) = K  K = 987663 cm-1
Ionization-energy Li : E = hc/ = 6.6∙10 ∙3∙10 ∙987663 = 1.96∙10-17 J = 122 eV
2+ -34 10

[dimensions: J s cm s-1 cm-1 = J ]

Balmer: (1/) = K{(1/n12) - (1/n22)}, n1 = 2
n2 = 3 1/ = 137175 cm-1
n2 = 4 1/ = 185184 cm-1
n2 =  1/ = K/n12 = 987663/4 cm-1

Extra: Hydrogenic, so no shielding; fill in Z = 3. Z2R = 987633 cm-1.

25
EXERCISE 1.7
Exercise: A particle of mass 6.65∙10-27 kg is confined to an infinite square well of width L. The energy
of the level to which n = 3 is 2.00∙10-24 J. Calculate the width of the box using the formula
given in Appendix 1.3.

Given: Particle, m = 6.65∙10-27 kg.

Infinite square well = one-dimensional box.
Energy level for n = 3 is 2.00∙10-24 J.

Needed: L

Strategy: Formula for a particle in a box; fill in the values for n, E, m and constants.

Solution: En = n2h2 /8mL2; L = 3(6.63∙10-34 J s)(8)-1/2(6.65∙10-27 kg)-1/2(2.00∙10-24 J)-1/2 = 6.10∙10-9 m

N.B.: You need the particle in a box formula for just the kinetic energy and the Rydberg-
series for the potential energy.

EXERCISE 1.8
Exercise: Calculate the energy difference between the levels with n = 4 and n = 5 of a deuterium
atom in a one-dimensional box of length 5.0 nm (see Appendix 1.3).

Given: Deuterium atom. One-dimensional box with L = 5.0 nm.

Needed: Energy difference between levels n = 4 and n = 5.
Strategy: Formula for a particle in a box for n = 4 should be subtracted from the formula for n = 5.
Note that you shouldn’t use n = 1!
Determine the mass of D: (md = mn + mp + me  2mp).
Solution: En = n2h2/8mL2; md = 2∙mp = 2∙1.67∙10-27 = 3.34∙10-27 kg.
E5,4 = (n52 - n42)(6.63∙10-34)2/8(3.34∙10-27)(5.0∙10-9)2 = 5.9∙10-24 J.

EXERCISE 1.9
Exercise: The first ionization energy for Li is 517.5 kJ mol-1. This corresponds to complete removal of
the electron from the nucleus, and is achieved when n = .
Calculate from this the effective nuclear charge felt by the 2s electron of Li by assuming
that the atom is hydrogen-like.
Why is this less than the actual nuclear charge of +3?

Given: IE1(Li) = 517.5 kJ mol-1.

IE1(Li) corresponds to the energy difference between n1=2 en n2=.
Zeff(Li 2s) < 3.

Needed: a) Zeff(Li 2s).

b) Why is Zeff(Li 2s) < 3?

Strategy: a) Find a formula for hydrogen-like atoms which relates Z (in this case Zeff) to the energy:
1/ = Zeff2R (1/n12 - 1/n22); ()E = hc/

N.B: You can also directly use E = -Zeff2Rhc/n12, like in the solution;
Find a relation between IE1 and energy (IE1 = -E).
What should be filled in for n1?

Solution: a) E = -Zeff2Rhc/n2; IE1 = -E; Zeff2 = IE1n2/Rhc = 517.5∙103∙4 / 1.1∙107∙1.986∙10-25∙6.02∙1023

 Zeff = 1.25 [dimensions: (J mol-1)/(m-1 J m mol-1)].
b) The 2s electron is shielded from the nucleus by the electrons in the 1s orbital.

26
EXERCISE 1.10
Exercise: Which of the following are possible sets of quantum numbers for an electron?
For the sets of quantum numbers that are not possible, state what is wrong with each set.

a) n = 1, l = 0, ml = 1, ms = +½ b) n = 9, l = 7, ml = -6, ms = -½
c) n = 2, l = 1, ml = 0, ms = 0 d) n = 1, l = 1, ml = 1, ms = +½
e) n = 3, l = 2, ml = -3, ms = +½ f) n = 4, l = 0, ml = 0, ms = -½

Given: Combinations of quantum numbers.

Needed: The possible combinations.

Strategy: Possible quantum numbers are: for n: from 1 to  (integer values);

for l: integers from 0 to n-1;
for ml: from -l to +l;
for ms: +½ and -½

Solution: a) Impossible: for l = 0, ml = 1 is not allowed.

b) Possible
c) Impossible: ms is never 0 for an electron.
d) Impossible: for n = 1, l = 1 is not allowed.
e) Impossible: for l = 2, ml = -3 is not allowed.
f) Possible

EXERCISE 1.11
Exercise: What is the maximum number of orbitals for n = 5? And for n = 4, l = 2?

Given: a) n = 5.
b) n = 4; l = 2.

Needed: Maximum number of orbitals.

Strategy: a) Determine which values of l belong to n = 5.

Determine all possible values of ml (2l+1) for each l.
Sum these values.
b) Determine the possible values of ml (2l+1) for l = 2.

Solution: n = 5: l = 0, 1, 2, 3, 4 and summation of ml (2l+1) gives:

(2∙0 + 1) + (2∙1 + 1) + (2∙2 + 1) + (2∙3 + 1) + (2∙4 + 1) = 25 = n2.
n = 4 and l = 2: the maximum number of orbitals is: 2∙2 + 1 = 5.

EXERCISE 1.12
Exercise: Compare the energy (in eV) of a single electron in a 3px orbital for H and Li2+.

Given: 3p(H) and 3p(Li2+).

Needed: Energy of 3p(H) and 3p(Li2+).

Strategy: Write down the electron configuration for both situations. You will see that both H and Li2+
are one-electron systems and the energy then only depends on n and Z.
Find a formula that relates E to n and Z.

Solution: E = -hcRZ2/n2 = -13.6 Z2/n2; for H (Z = 1) and n = 3: E = -13.6/9 = -1.51 eV;

for Li2+ (Z = 3) and n = 3: E = -13.6 eV

Extra: Can you show that hcR = 13.6 eV ? (see Appendix 1.4).

27
EXERCISE 1.13
Exercise: How many levels in hydrogen have energy (a) -hcR, (b) -hcR/9, and (c) -hcR/25?

Given: Hydrogen atom, energy is subsequently -hcR, -hcR/9, -hcR/25.

Needed: The number of levels that corresponds to a certain energy.

Strategy: l = 0, ...., n-1. Number of levels for a certain l = 2l+1, can be determined using n.
Find a formula that relates E to n.
Hydrogen atom, so: Z = 1.

Solution: The number of levels for a certain l = 2l+1; E = -hcR/n2

for E = -hcR n = 1, l = 0  2l+1 = 1

for E = -hcR/9 n = 3, l = 2  2l +1 = 5 
l = 1  2l +1 = 3  total: 9
l = 0  2l+1 = 1 

for E = -hcR/25 n = 5, l = 4  2l+1 = 9 

l = 3  2l+1 = 7 
l = 2  2l+1 = 5  total: 25
l = 1  2l+1 = 3 
l = 0  2l+1 = 1 

EXERCISE 1.14
Exercise: How many electrons can occupy the following orbitals:

(a) 1s (b) 3p (c) 3d (d) 6f

Given: subsequently 1s, 3p, 3d, 6f.

Needed: Number of electrons that can occupy the specific orbital.

Strategy: Total number of electrons in an orbital is 2.

Determine the number of orbitals for the given type.
Determine the number of electrons that can be placed in the orbitals.

Solution: 2∙(2l+1), so: a) 2 b) 6 c) 10 d) 14

28
Solutions to the exercises accompanying Part 2

EXERCISE 2.1
Exercise: What is the ground-state electronic configuration of the atoms with the atomic numbers
7, 20, 26, 32?

Given: Atomic numbers.

Needed: Electron configuration of the ground state.
Strategy: Write these down, taking into account the filling of (n+1)s prior to nd.
Often, the abbreviated notation is used, so only the valence electrons aren’t abbreviated.

Solution: 7 N: 1s22s22p3 or: [He]2s22p3

20 Ca: 1s22s22p63s23p64s2 or: [Ar]4s2
26 Fe: 1s22s22p63s23p64s23d6 or: [Ar]4s23d6
32 Ge: 1s22s22p63s23p64s23d104p2 or: [Ar]4s23d104p2

EXERCISE 2.2
Exercise: Give the electronic configurations of P, Mn, Te2-, Cr2+, Co2+, Mo4+, Ir3+, Cu2+and Cu+ (see
Appendix 2.2).

Given: Symbols of elements and ions.

Needed: Electron configuration of the ground state.

Strategy: Write down the electron configuration.
Be warned: for the positively charged transition metal ions, first transfer the s-electrons to
the d-orbitals, and then remove the necessary number of electrons from the d-orbitals.
Often, the abbreviated notation is used, so only the valence electrons aren’t abbreviated.

Solution: P: [Ne]3s23p3 Mn: [Ar]4s23d5 Te2-: [Kr]5s24d105p6

Cr2+: [Ar]3d4 Co2+: [Ar]3d7 Mo4+: [Kr]4d2
Ir3+: [Xe]4f145d6 Cu2+: [Ar]3d9 Cu+: [Ar]3d10

EXERCISE 2.3
Exercise: Arrange the following groups of atoms in order of increasing size and first ionisation energy
(see Appendix 2.3):

a) Be, Mg, Ca b) Te, I, Xe c) Ga, Ge, In d) As, N, F e) S, Cl, F

Given: Groups of atoms.

Needed: Within the group, order the atoms by size.

Within the group, order the atoms by first ionization energy.

Strategy: Determine what the trend in radii and ionization energies is.
Write down the electron configurations and reason, based on this, what the order should be.

Solution: Radii: In a group, downwards, the radius becomes larger. Z is getting larger, but apparently
Zeff does not increase enough to compensate for the increasingly large n. In a given period,
n is constant, but when going to the right, Zeff will increase, so the radius becomes smaller.
This results in: Be < Mg < Ca; Xe < I < Te; Ge < Ga < In; F < N < As; F < Cl < S.
First ionization energies: in a period from left to right, IE1 globally increases. The effective
nuclear charge increases, because Z is not completely shielded by electrons with the same
main quantum number. In a group IE1 decreases, because n increases and electrons in a
shell with higher n are farther away from the nucleus. Z also increases, but this effect is
less important. Note that for these cases the spin-pairing energy is not relevant.
The result is: Ca < Mg < Be; Te < I < Xe; In < Ga < Ge; As < N < F; S < Cl < F.

29
EXERCISE 2.4
Exercise: Why is the first ionization energy of the oxygen atom lower than that of the nitrogen atom?

Data: IE1(O) < IE1(N)

Needed: Why is IE1(O) < IE1(N)?

Strategy: Write down the electron configuration for both atoms.

Determine if the general trend is valid, and if not, give a reason for this.

Solution: There’s a global increase of ionization energy to the right in a row of the Periodic Table. In
nitrogen, a sub-shell is half filled. Adding an electron, going from N to O, means that Z
increases, but spin-pairing energy is also needed to place this extra electron. This last
effect is more important, and thus less energy is needed to remove an electron from O.

EXERCISE 2.5
Exercise: Explain the trend in ionization energies for the noble gases.

Given: There is a trend in IE1 for the noble gases.

Needed: What is this trend?

Strategy: Determine what the general trend in IE1 is.

Solution: The ionization energy in a group of the Periodic Table decreases from top to bottom. Z
increases, but the electron is also located further way from the nucleus. The effect of the
increase of r is, looking at the experimental data, more important than the increase of Z,
and as such, ionization becomes easier going to the bottom.

EXERCISE 2.6
Exercise: For each of the following sets write down the atoms in the order of increasing first
ionization energies.
Give arguments for your choice.

a) Be, N, F b) Be, Ca, Ba c) Be, B, C

d) N, O, F e) F, Cl, Br f) Si, P, S

Given: A set of atoms.

Needed: Sort the atoms within the set by increasing IE1.

Strategy: Determine the general trend in IE1.

Write down the electron configuration.
Determine, based on this data, the order of the atoms.

Solution: a) Be < N < F: configuration resp. [He]2s2, [He]2s22p3, [He]2s22p5; there is an increase of
the ionization energy to the right of a row because Z becomes larger during filling of the
orbitals with the same n.
b) Ba < Ca < Be: configuration resp. [Xe]6s2, [Ar]4s2, [He]2s2; Decrease of ionization
energy in a group because of the increasing r, which is more important than increase in Z.
c) B < Be < C: configuration resp. [He]2s22p1, [He]2s2, [He]2s22p2; from Be to B: transition
to a new quantum number l, ionization-energy smaller, from B to C the increase of Z is
dominant because filling occurs for the same quantum number I.
d) O < N < F: configuration resp. [He]2s22p4, [He]2s22p3, [He]2s22p5; There is a global
increase of the ionization energy to the right of a row. After a half filled shell (N), the
ionization energy decreases because of the spin pairing energy which is needed to place
the last electron. The effect of this last spin pairing energy is larger than the increase of Z.

30
 e) Br < Cl < F: configuration resp. [Ar]4s24p5, [Ne]3s23p5, [He]2s22p5; in a group the
ionization energy decreases downwards because n increases, and so does r. The effect of
the increasingly large Z does not compensate for the increase in r.
f) Si < S < P: configuration resp. [Ne]3s23p2, [Ne]3s23p4, [Ne]3s23p3; see explanation at d).

EXERCISE 2.7
Exercise: Which atom in the following pairs has the highest IE1? Al or Mg; Zn or Ca? Explain why.

Given: Pairs of atoms.

Given: For each pair, determine which atom has the highest IE1, and explain why.

Strategy: Write down the electron configuration of the atoms and determine, based on this, which
atom has the highest IE1.

Solution: IE1 of Mg (electron configuration: [Ne]3s2) is larger than IE1 of Al (electron configuration:
[Ne]3s23p1); 3p has a higher energy than 3s.
IE1 of Zn (electron configuration: [Ar]3d104s2) is larger than IE1 of Ca (electron
configuration: [Ar]3d04s2); Zn has a higher nuclear charge, which is only partially shielded
by the electrons in the 3d orbitals.

Extra: d-orbitals are diffuse compared to s and p-orbitals. A diffuse orbital means that the electron
density is spread out over a larger space, meaning that at every point, the electron density
is small.

EXERCISE 2.8
Exercise: In a sodium atom the valence electron has been promoted to an excited 4s state. Is this
excited electron easier or harder to remove than the valence electron in potassium? Explain!

Given: Excited Na atom, valence electron is not in 3s but in 4s. K atom is in the ground state.

Needed: Is the 4s electron harder or easier to remove from Na than from K and why?

Strategy: Write down the electron configuration of the excited Na state and the ground state of K.
Determine in which case the shielding of the nuclear charge is the smallest.

Solution: K 1s22s22p63s23p64s1;
Na 1s22s22p6
* 4s1
The 4s electron of Na experiences a smaller effective charge than that of K because the
electron cloud of the 3s and the 3p can’t fully shield the 8 extra proton charges in K.
This is why the electron from Na* will be the easiest one to remove.

EXERCISE 2.9
Exercise: Show that there are several possible Lewis structures (see Appendix 2.4) for the chlorate
anion, ClO3-.
Indicate the formal charges of the atoms (see Appendix 2.5).
Point out where the octet rule (see Appendix 2.7) isn’t fulfilled and give a brief justification.
Predict the geometry based on VSEPR theory.

Given: ClO3-

Needed: Resonance structures, formal charges.

Is the octet rule satisfied, or is this not necessary? Give the geometry.

Strategy: Count the number of electrons surrounding the atoms.

Determine whether or not the octet rule should be satisfied.
Give the definition of the formal charge and calculate this for each atom.

31
Solution: The most likely structures are those with a negative charge on one of the O atoms. To
solve a charge problem, the octet rule may be disregarded on Cl because Cl isn´t a first or
second row element. The geometry of electron regions surrounding Cl in ClO3- is
tetrahedral. The geometry (molecular shape) of the ClO3- ion is trigonal pyramidal.

EXERCISE 2.10
Exercise: Predict, using the VSEPR theory, the structure of H2NOH (hydroxylamine), BaCl2, XeO2F2,
(CH3)2SeO, and (H2N)2CO (urea).
Indicate for all compounds whether the angles are more obtuse, more acute, or equal to that
of the ideal basic arrangement.
Indicate, where applicable, the most important resonance structures.
Explain all answers.

Given: H2NOH (hydroxylamine), BaCl2, XeO2F2, (CH3)2SeO, and (H2N)2CO (urea).

Needed: Structure and deviations from the ideal geometry.

Strategy: Determine what the ideal angles for the structures are and adjust them according to the
rules on page 38 IC.

Solution: H2NOH: total of 14 electrons 7 ep

 electron pair arrangement is tetrahedral, structure around N is a
(malformed) trigonal pyramid; around O: electron pair arrangement
tetrahedral, structure around O is V-shaped (or bent).

BaCl2: 16 electrons  8 ep
structure is linear, angles 1800.

XeO2F2: total of 34 electrons  17 ep;

ep-arrangement tbp: lp and O atoms in equatorial plane, F axial (single
versus double bonds); OXeO angles in equatorial plane < 120o because
of the lp. FXeO angles < 90o.
Molecular shape of this molecule is seesaw.

(CH3)2SeO: 26 electrons  13 ep;

electron pair arrangement tetrahedral, CSeC and OSeC angles < 109.5o;
OSeC angles are larger than the CSeC angle because of the double bond
repulsion. Shape of this molecule is trigonal pyramidal.

(H2N)2CO: 24 electrons  12 ep;

shape around N trigonal pyramidal (malformed); shape around C
triangular planar, because of repulsion double bond, angle NCN < 120o.

32
EXERCISE 2.11
Exercise: Write down the electronic structural formulas for each of the following molecules.
Your formulas should include formal charges, if any, and reasonable resonance structures.
Mention the geometrical arrangement of the atoms around the central atom.

a) SO42- b) CH3COO- c) ClF3 d) SF4 e) HNO3 f) PO43-

Given: a) SO42- b) CH3COO- c) ClF3 d) SF4 e) HNO3 f) PO43-

Needed Lewis structures, formal charges.

Strategy: See Appendix 2.4 and 2.5

(strategy).

Solution: a) SO42-: 32 electrons 16 ep 

tetrahedral arrangement around S;
to minimize formal charges: S with
two O- and two O; the structures
shown are most important.

b) CH3COO-: 24 electrons; trigonal planar around

carboxylic C; tetrahedral around methyl-C.

c) ClF3: 28 electrons indicate a tbp geometry around Cl for the electron

regions where two positions in the equatorial plane are occupied by lone
pairs. The angles FClF are smaller than 90o/180o. Molecular shape is t-shape.

d) SF4: 34 electrons around S: electron pair arrangement has a tbp geometry with in
the equatorial plane a lone pair; F atoms are bent towards each other. Shape is
seesaw.

e) HNO3 = NO2(OH): total of 24 electrons; a neutral N

doesn’t satisfy the octet rule; better would be N+ with
O, O- and OH, meaning there is a trigonal planar
geometry around N. Around O (in OH) there is a
tetrahedral arrangement of ep’s, structure is V-shaped.
The angle HON will probably be smaller than 109.5o.
The ONO angle (O not being part of the OH group) will probably be larger than 120o.

f) PO43-: 32 electrons indicate a tetrahedral arrangement of the electron regions around P.

Octet expansion is possible for phosphorus. The most important structure is P with three O-
and one O; the tetrahedral geometry of the ep's remains intact; all OPO angles are
identical because of resonance. Molecular shape is also tetrahedral.

33
EXERCISE 2.12

Exercise: Which of the following structures (connectivities) of N2F4 found below is the most stable one?
Explain your answer using Lewis structures.

(Note that the dashes indicate bonds, although these need not necessarily be single bonds.)

Apart from NF3, PF3 and PF5, NF5 also exists. What is the electronic structure of this last
compound? What is its geometry?

Given: Some possible structures for N2F4.

NF5.

Needed: Most stable structure for N2F4.

Structure for NF5.

Strategy: Count the total number of electrons in the compound and distribute these amongst the
atoms according to the rules for the construction of Lewis structures.
Determine the formal charges and determine which structure has the fewest and smallest
formal charges. To find the structure of NF5 one must first conclude that the octet rule can´t
be exceeded on N, and therefore only an ionic structure is possible.

Solution:

 most stable,
no formal charges

NF5 = [NF4]+F- is an ionic compound with a tetrahedral structure of F atoms around N.

EXERCISE 2.13
Exercise: Which of the following triatomic molecules and ions are expected to be linear:

(a) CO2 (b) NO2+ (c) NO2- (d) SO2 (e) H2O (f) H2O2+?

Given: (a) CO2 (b) NO2+ (c) NO2- (d) SO2 (e) H2O (f) H2O2+

Given: Which compounds have a linear structure?

Strategy: Determine the Lewis structures.

Determine how many electron pairs the central atom has.

Solution: CO2 and NO2+ have a linear geometry, the other molecules don’t: NO2-, SO2 and H2O2+
have a trigonal planar arrangement of ep’s on the central atom and their geometry is bent.
H2O has a tetrahedral arrangement of ep’s on oxygen and its geometry is bent.

Extra: NO2+ : angle is 180o; NO2- : angle is 115o.

34
EXERCISE 2.14
Exercise: Draw the three most important resonance structures for cyanogen azide, CN4, given that
the atoms are bonded in the order NNNCN. Indicate all valence electrons and formal
charges. Can you predict whether the molecule will be bent or linear?

Given: CN4.

Needed: Important resonance structures.

Is the molecule bent or linear?

Strategy: Determine the Lewis structures.

Determine how many electron pairs the central atoms have.

Solution: Total of 24 electrons; 8 electrons are needed for single bonds: 16 electrons are left. Give
the atoms at the end an octet, which leaves 4 electrons, these can for example be put on
the N in the middle; with formal charges on all atoms the initial trial structure becomes:

Shuffling the electron pairs around in a “wise” manner yields some meaningful resonance
structures, wherein all atoms have an octet: b, c and e are the most likely, with an angle
smaller than 180o around the N in the middle, the third atom from the left. Structure is bent.

EXERCISE 2.15
Exercise: The structure of the pentafluorotellurate monoanion [TeF5]-1 has been determined by X-ray
techniques.
What is the oxidation number of Te in this anion?
Draw the Lewis structure for the anion.
Determine the geometry and explain any deviations from ideal geometry.

Given: The pentafluorotellurate monoanion.

Needed: Oxidation number of tellurium in this ion.

The Lewis structure.
The geometry and any deviations from the (ideal) geometry.

Strategy: Give the definition of the oxidation number.

Determine the oxidation number.
Determine the Lewis structure.
Determine the ideal angles of the structure, and see if these are perturbed by lone pairs
and/or multiple bonds.

Solution: [TeF5]-: oxidation number of Te is IV; total of 42 electrons  6

ep on Te. Geometry for the electron regions is octahedral and
the molecular shape is square pyramidal. It is expected that the
F atoms forming the base plane of the pyramid are bent to the
F on the top of the pyramid because of the lone pair repulsion.

35
Solutions to the exercises accompanying Part 3
EXERCISE 3.1
Exercise: When a bond is formed between two atoms, they are drawn together. What limits their
internuclear distance so that they do not coalesce?

Given: A bond is formed between two atoms.

Needed: Why don’t the nuclei coalesce?

Strategy: Determine what the attractive and repulsive forces between the atoms are.

Solution: The nucleus-nucleus repulsion prevents the atoms from coalescing.

EXERCISE 3.2
Exercise: In a compound A-B, on both the A and B atom s and p-orbitals are available for the
formation of molecular orbitals. Choose a coordinate system (take the z-axis as the line
between both nuclei) and indicate which atomic orbitals, based on their symmetries,
combine to give bonding molecular orbitals. Indicate whether these combinations are of the
 or  type.

Given: Compound A-B; atom A: s and p-orbitals, atom B: s and p-orbitals.

Needed: Which orbitals on A overlap with orbitals on B in a manner that bonds are formed? Are
these bonds of the  or  type?

Strategy: Pick a coordinate system and put the nuclei of A and B on some distance from each other.
Generally, the best choice is to choose a unique axis as the z-axis; for a diatomic system,
the z-axis will correspond with the line between the two nuclei.
Once a coordinate system has been chosen, it can’t be changed while the problem is being
solved! Draw the orbitals on B and let all orbitals of A subsequently approach those of B in
a correct manner (make sure the nuclei don’t coalesce!). Determine which combinations
have the same sign when overlapping. Rotate the binding combinations around the z-axis
and determine if any nodes are passing during the rotations: no nodes indicate a -bond,
one node indicates a -bond.

Solution: If the molecular axis is chosen as the z-axis, there is  overlap between the s[A] and s[B],
s[A] and pz[B], pz[A] and s[B], pz[A] and pz[B] orbitals. There is  overlap between the px[A]
and px[B] and between the py[A] and py[B] orbitals.

EXERCISE 3.3
Exercise: Which of the molecules N2, NO, O2, C2, F2 and CN would you expect to be stabilized by
(a) the addition of an electron to form AB- (b) the removal of an electron to form AB+

Given: N2, NO, O2, C2, F2 and CN.

Needed: Which of the molecules become more stable when a) adding an electron, b) removing an
electron.

Strategy: Bondorder and stabilization are connected for similar molecules: if the bondorder increases
as an electron is added or removed, the compound will become more stable; if the
bondorder decreases, the compound becomes less stable. The bondorder can be
determined from the MO diagram of the molecule.

Solution: Adding an electron stabilizes C2 and CN;

Removing an electron stabilizes NO, O2 and F2;
N2 is destabilized by both the addition and removal of an electron.

36
EXERCISE 3.4
Exercise: True or false: The set of valence shell orbitals (2s, 2p) for N are of higher energy than
those for C. Explain your answer.

Given: Valence-orbitals of N and C.

Needed: Is it correct that the valence orbitals of N are higher in energy than those of C?

Strategy: Determine which factors influence the energy of the orbitals and how these factors affect
the energy levels.

Solution: Because the effective nuclear charge of N is larger than that of C, the valence orbitals of N
are lower in energy than those of C. Therefore, the statement in the question is false.

EXERCISE 3.5
Exercise: Sketch the molecular energy level diagram for XeF. The energy of Xe 5s is similar to F 2s
and the energy of Xe 5p is similar to F 2p. Neglect the overlap between s and p-orbitals. Is
XeF likely to have a shorter bond length than XeF+?

Given: XeF

Needed: MO-diagram of XeF.

What happens to the bond length of XeF when an electron is removed?

Strategy: Determine the geometry of the compound and choose a coordinate system.
Determine which combination of atomic orbitals, with respect to their symmetries and
energies, are suited for forming a molecular orbital. Determine the symmetry type of the
molecular orbitals found. Draw the MO diagram.
Check whether the number of MOs is equal to the number of AOs.
Put the correct number of electrons in the MO diagram.

Solution: The atomic orbitals important for forming molecular orbitals are 5s and 5p for Xe, and 2s
and 2p for F. The bond scheme and MO diagram then becomes:

Xe F XeF
5px ± 2px , *
5py ± 2py , *
5pz ± 2pz , *
5s ± 2s , *

XeF+ has a larger bondorder than XeF

(electron is removed from an anti-bonding
MO), and as such a stronger bond and a
shorter bond length is expected for XeF+.

EXERCISE 3.6
Exercise: What is the bondorder of Hg22+ and how
does this change when the ion is reduced
or oxidized?

Given: Hg22+

Needed: The bondorder of Hg22+.

Change of bondorder from Hg22+ to Hg2+.
Change of bondorder from Hg22+ to Hg23+.

Strategy: The bondorder can be determined using the MO diagram of the compound, where only the
overlap of valence orbitals is important. See Appendix 3.1 and EXERCISE 3.5 (strategy).

37
Solution: Hg: [Xe]4f145d106s2  Hg+: [Xe]4f145d106s1  only 6s is
relevant. The bond scheme and MO diagram is:

Hg+ Hg+ Hg22+

6s ± 6s , *

Hg22+, BO = ½(2-0) = 1 ;
After reduction Hg2+, BO = ½(2-1) = ½.
After oxidation Hg23+, BO = ½(1-0) = ½.

EXERCISE 3.7
Exercise: In a compound A-B, the d-orbitals in A and the p-orbitals in B are available for the
formation of molecular orbitals. Choose a coordinate system (take the z-axis as the line
between both nuclei) and indicate which atomic orbitals, based on their symmetries,
combine to give bonding molecular orbitals. Indicate whether these combinations are of the
 or  type.

Given: Compound A-B; atom A: only d-orbitals, atom B: only p-orbitals.

Needed: Which d-orbitals on A overlap with p-orbitals on B to form bonds?

Are the bonds that are formed of the  or  type?

Strategy: Choose a coordinate system and place the nuclei of A and B on some distance from each
other. It is good practice to choose the unique axis as the z-axis. For a diatomic molecule,
the z-axis is the same as the line between both nuclei. As soon as the coordinate system
has been chosen, this must not be changed while solving the problem!
Draw the orbitals on B and let all orbitals of A subsequently approach those of B in a
correct manner (make sure the nuclei don’t coalesce!). Determine which combinations
have the same sign when overlapping. Rotate the binding combinations around the z-axis
and determine if any nodes are passing during the rotations: no nodes indicate a -bond,
one node indicates a -bond.

Solution: If the bond axis is chosen as z-axis, there is  overlap between the dz2[A] and pz[B] orbitals
and  overlap between the dxz[A] and px[B] and between the dyz[A] and py[B] orbitals.

EXERCISE 3.8
Exercise: Give the ground state electronic configurations and bondorders of respectively C2, H2-, O2,
NO, and CN-.

Given: C2, H2-, O2, NO, CN-.

Needed: Electron configuration for the ground state.

Strategy: Determine which orbitals overlap. Determine which orbitals participate in bonding and anti-
bonding and draw the MO diagram. Fill the MO diagram with electrons.

Solution: For H2-, only the 1s-orbitals of both H-atoms are important. They form a  and * bond.
H2- [(1s)]2[(1s)* ]1; BO=1/2.
For the other atoms or ions, the 2s and 2p orbitals are important.
Orbital mixing of s and p will take place for C2 and CN- and is maybe possible for NO; for
O2 s-p orbital mixing is not relevant.

C2: [(1)]2[(2)* ]2[(2p)]4, BO=2.

O2: [(2s)]2[(2s)* ]2[(2p)]2[(2p)]4[(2p)* ]1[(2p)* ]1, BO=2.
NO: [(2s)]2[(2s)* ]2[(2p)]2[(2p)]4[(2p)* ]1 or [(1)]2[(2)* ]2[(2p)]4[(3)]2[(2p)* ]1
depending on whether s-p orbital mixing is taken into account: BO=2.5.
CN-: [(1)]2[(2)* ]2[(2p)]4[(3)]2, BO=3.

38
 Note: Molecular orbitals where s-p orbital mixing is present are numbered; they are no
longer formed by atomic orbitals of only one specific type.

EXERCISE 3.9
Exercise: From the ground state electronic configurations of B2 and C2 predict which molecule should
have the greater bond dissociation energy.

Given: B2 and C2 in the ground state.

Needed: Which molecule has the highest bond-dissociation energy.

Strategy: Bond-dissociation energy is dependent on the bond strength, which in turn depends on the
bondorder (for similar molecules) {= ½(the number of electrons in bonding orbitals – the
number of electrons in anti-bonding orbitals)}. The bondorder can be determined from the
MO diagram of the molecule.

Solution: B2: [(1)]2[(2)* ]2[(2p)]2, BO = 1; C2: [(1)]2[(2)* ]2[(2p)]4, BO = 2.

From the bondorder, it follows that C2 has the highest bond-dissociation energy.

Note: Molecular orbitals where s-p orbital mixing is present are numbered; they are no
longer formed by atomic orbitals of only one specific type.

EXERCISE 3.10
Exercise: Draw an MO diagram of the molecule LiF and discuss based on the diagram the bondorder
and the polarity.

Given: LiF

Needed: MO diagram of LiF.

What is the bondorder of LiF.
What is the polarity of LiF.

Strategy: See Appendices 3.1 and 3.2 and EXERCISE 3.5 (strategy).
Take into account the difference in atomic orbital energies for Li and F.
The polarity is a direct consequence of the difference in orbital energies.
The bondorder can be determined from the MO diagram {= ½(the number of electrons in
bonding orbitals – the number of electrons in anti-bonding orbitals)}.

Solution: Li: 1s22s1, F: 1s22s22p5; If we assume that

the overlap of F 2s with the Li orbitals is
negligible (because of an energy difference
larger than 15 eV) and the p-orbitals of Li
don’t participate (too high in energy), the
bonding scheme and MO diagram becomes:

Li F LiF
2s ± 2pz , *
2px nb(F 2px)
2py nb(F 2py)
2s nb(F 2s)

Polarity: the contribution of F in  bonding

is much larger than that of Li. This means
that the  bond is mostly of the F 2p type.
So: the electron density for this bond is
mostly localized on F: Li+F-.
BO = ½(2-0) = 1.

39
EXERCISE 3.11
Exercise: Describe the bond in H2O2 using hybrids and create a qualitative MO diagram.

Given: Molecule H2O2.

Needed: A description of H2O2 and an MO diagram.

Strategy: Determine the Lewis structure and geometry using VSEPR theory. Then determine the
correct hybridization type and construct an MO diagram.

Solution: First determine the structure from VSEPR using the Lewis structure of HOOH.
O: 6 ve; H: 1 ve; total of 14 ve  7 ep  tetrahedrons (with 2 lp) on the O’s and thus
describe the O’s using sp3 hybrids.

H O O H HOOH
1s ± sp3 sp3 ,*; nb(O sp3)
sp3 sp3 ± 1s nb(O sp3); ,*
sp3 ± sp3 ,*
sp3 sp3 nb(O sp3); nb(O sp3)

There’s a total of 14 electrons which must be placed in the MO diagram.

EXERCISE 3.12
Exercise: CO2, HgCl2 and (CN)2 are linear.
Draw Lewis structures and assign hybridizations for each atom.

Given: CO2, HgCl2 and (CN)2 are linear.

Needed: The Lewis structures and corresponding hybridizations for each atom.

Strategy: Determine the atom sequence.

Count the total number of available electrons in the valence shells.
Place an electron pair in each bond.
Give the peripheral atoms as many electrons as needed to ensure they reach the noble
gas configuration. Place the remaining electrons in pairs on the non-peripheral atoms.
Complete, if needed, the octets by forming bonds on non-peripheral atoms.
Minimalize, by shuffling the electron pairs, the formal charges.

Note: exceeding the octet rule for second row atoms is forbidden.
Determine hybridization using the number of electron regions around an atom, where
double or triple bonds count only once.

40
Solution: CO2 HgCl2 (CN)2
4+2∙6 = 16 electrons 2+2∙7 = 16 electrons 2∙(4+5) = 18 electrons
 8 ep  8 ep  9 ep

EXERCISE 3.13
Exercise: Draw a qualitatively correct energy-level diagram for the CO2 molecule using only
hybridization for the carbon atom. Show that it accounts correctly for the presence of
double bonds.

Given: CO2.

Needed: MO diagram.

Strategy: See EXERCISE 3.12 and Appendix 3.1.

Solution: CO2 structure (see EXERCISE 3.12) is linear:

O C O CO2
2pz ± sp ,*
sp ± 2pz ,*
2px 2px ± 2px nb(O 2px), , *
2py ± 2py 2py , *, nb(O 2py)
2s 2s nb(O 2s), nb(O 2s)

Note: The 2s orbitals of the O atoms do not participate in bonding (because of their orbital
energy).

BO: ½(8 - 0) = 4 per 2 CO bonds: each CO bond is a double bond.

41
EXERCISE 3.14
Exercise: Give a description of NO2-
a) Using the possible Lewis structures.
b) Using an MO diagram. Use hybridization on all atoms.
Why do you need two MO diagrams to describe NO2- ?

Given: NO2-

Needed: Lewis structures. MO diagram.

Strategy: Follow the strategy in EXERCISE 3.12 for the determination of the Lewis structure.
Note that there might be distinct resonance structures.
For the MO diagram, follow the steps in EXERCISE 3.5 (strategy).

Solution: VSEPR NO2- : 5+2∙6+1 = 18 electrons 9 ep.

Adjustment (a) is incorrect: N violates the octet rule. The right adjustment (b) yields two
structures with a triangular planar electron arrangement. In both cases you have one lone
pair on N and a total of five lone pairs on the two O's together. Hybridization N: sp2; the two
O atoms have two different hybridization states (sp2 and sp3). A localized MO description
for only one resonance structure can be constructed, and thus in principle you need two
MO diagrams to describe the overall situation in NO2- (in which you label the O atoms):

O N O ONO
sp3 ± sp2 sp2 , *, nb(O sp2)
sp3 sp2 ± sp2 nb(O sp3), , *
sp3 sp2 sp2 nb(O sp3), nb(N sp2), nb(O sp2)
sp3 2pz ± 2pz nb(O sp3), , *

Note: From Lewis structures of NO2- : 18 electrons; BO 1½, per bond. The bondorder per bond is
the average of all bondorders in the resonance structures.
The bondorder of NO2- calculated from the MO diagram is 3: BO 1½, per bond!

42
EXERCISE 3.15
Exercise: Give an MO diagram for CO32-, with a fully localized description and using hybridization on
both C and O and add the right number of electrons. Calculate the bondorder using the MO
diagram. What will be the MO diagram of CO32- when you describe the σ-skeleton and -
system separately, using hybrids for the σ-skeleton and SALCs for the -system?

Given: CO32-

Needed: MO diagram

Strategy: See EXERCISE 3.12 (strategy).

Solution: CO32-: 24 electrons 12 ep.

Keep in mind the number of double bonds surrounding C!  OC(O-)2  hybridization
around both O-'s is sp3, around O sp2 (see structure).

O O C O CO32-
sp3 ± sp2 , *
sp3 sp3 ± sp2 nb, , *
sp3 sp3 sp2 ± sp2 nb, nb, , *
sp3 sp3 sp2 nb, nb, nb
sp3 sp2 nb, nb
2pz ± 2pz , *

MO diagram fully localized description:

The bondorder of CO32- is:

BO = ½(8 - 0) = 4 per 3 CO bonds. Bondorder is 4/3 per bond.

43
Now: describe σ-skeleton and π-system separately.

σ-skeleton: all three O’s are sp2 hybridized:

C O O O
sp2 ± sp2 , *
sp2 ± sp2 , *
sp2 ± sp2 , *
sp2 sp2 sp2 nb, nb, nb
sp2 sp2 sp2 nb, nb, nb

MO diagram of (only) the σ-skeleton:

π-system: a SALC can be constructed that combines optimally with the 2pz of C:

SALC1 = O 2pz + O 2pz + O 2pz.

The remaining SALCs should be non-bonding.

The MOs of the π-system are:

C 2pz ± SALC1(O 2pz + O 2pz + O 2pz ) , *

SALC2(O 2pz .. O 2pz .. O 2pz ) nb
SALC3(O 2pz .. O 2pz .. O 2pz ) nb

MO diagram of the π-system:

44
EXERCISE 3.16
Exercise: Draw Lewis structures for O3 (ozone) and SO2.
For ozone,  OOO = 117o. For sulfur dioxide  OSO = 120o. Explain this difference in
bond angles. Formulate a molecular orbital description for the -skeleton of the ozone
molecule using hybridization for all oxygen atoms. Describe the -system separately using
SALCs.

Given: O3 and SO2

Needed: Lewis-structures.
MO diagram constructed using hybrids.

Strategy: For drawing the Lewis structures see EXERCISE 3.12 (strategy)
For the MO diagram see EXERCISE 3.5 (strategy)

Solution: Resonance structures:

The angle OSO > OOO (angles resp: 119.5o and 116.5o). Because of the third resonance
structure of SO2, double bond – double bond repulsion is partly involved. This explains the
larger angle in SO2 compared to O3.
O3: central O sp2 hybridization. On terminal O's sp2 should be chosen if the σ-skeleton and
the π-system are described separately.

The σ-skeleton:

O O O O3
sp2 ± sp2 , *
sp2 ± sp2 , *
sp2 sp2 nb, nb
sp2 nb
sp2 nb
sp2 nb

MO diagram of (only) the σ-skeleton:

45
 MOs of the π-system:

O O,O O3
2pz ± SALC1(O 2pz + O 2pz) , *
SALC2(O 2pz – O 2pz) nb

MO diagram of the π-system:

Extra: Combining the two MO diagrams for the σ-skeleton and the π-system leads to the following
overall MO diagram for the ozone molecule:

Extra: Fully localized: choose for O- an sp3 hybrid and for the terminal (neutral) O an sp2 hybrid.
The result doesn’t differ much from the above diagram.
The use of SALCs shows that the electrons in the double bonds are delocalized. This can
also be concluded from the combination of resonance structures in the Lewis description.

46
EXERCISE 3.17
Exercise: The cyanate ion can be represented as: CON-, CNO- or OCN-.
Use Lewis structures to determine which of the formulas above describes the most stable
compound. Construct a localized MO diagram for this ion.

Given: Ion consists of C, N, O in a 1:1:1 ratio.

Needed: Most stable structure of this ion.

MO diagram of the most stable ion.

Strategy: Determine the resonance structures of the ion for all atom orders (see EXERCISE 3.12 for
strategy).
Determine for each resonance structure the formal charge on each atom.
Determine which set of resonance structures has the lowest formal charges.
For the MO diagram see EXERCISE 3.5 (strategy).

Solution: The ions have 16 electrons. For CNO- the initial trial Lewis structure, where all bonds
contain an electron pair and all terminal atoms satisfy the octet rule, is:

To also give the central atom an octet, two π-bonds are needed. By shuffling the lone
pairs, the resonance structures can be determined. The procedure is analogous for the
other atom orders. Resonance structures:

Stable compounds should have resonance structures satisfying:

 As few formal charges as possible
 If possible, no multiple formal charges on a single atom.
 If possible, no same sign formal charges next to each other.

Based on these rules, it is expected that OCN- is the most stable one, and that this ion is
mostly in resonance states b and c. For the MO diagram we choose structure c (with
localized MOs) and the geometry around the atoms should first be determined. The
electron ordering around C is linear and sp hybridization should be chosen for this atom. O
and N should respectively be sp3 and sp hybridized.

O C N OCN-
sp3 ± sp , *
sp ± sp , *
sp nb
2px ± 2px , *
2py ± 2py , *
sp3 nb
sp3 nb
sp3 nb

47
 The MO diagram for OCN-:

EXERCISE 3.18
Exercise: Explain in detail, using both the MO approach and the resonance theory, why the NO
bonds in NO3- have a bondorder of 4/3. Give the MO diagram for one of the Lewis
structures using hybrids only.

Given: NO3-.

Needed: Why is the bondorder 4/3 per bond (explain using MO theory and Lewis structures).

Strategy: See EXERCISE 3.14.

Solution: The three resonance structures of NO3- are drawn below:

Every resonance structure has a -bond between N and every O. The -bond is spread out
across three positions. Bondorder per bond is therefore 4/3 according to resonance theory.

MO description: sp2 hybridization on N; note that the best description is using N+, two O-
and one O. This leads to sp2 hybridization around O and sp3 hybridization around O-.

N O O O NO3-
sp2 ± sp2 , *
sp2 ± sp3 , *
sp2 ± sp3 , *
sp2 sp3 sp3 nb, nb, nb
sp2 sp3 sp3 nb, nb, nb
sp3 sp3 nb, nb
2pz ± 2pz , *

48
MO diagram NO3- :

BO of NO3- from MO diagram = 4. This is for all bonds together. According to the MO
approach the bondorder is also 4/3 per bond!

49
Solutions to the exercises accompanying Part 4

EXERCISE 4.1
Exercise: By using orbital splitting diagrams, show which dn electronic configurations are capable of
giving either low-spin or high-spin configurations in an octahedral crystal field.

Given: Octahedral crystal field.

Needed: Which configurations can be either high or low spin?

Strategy: Draw an octahedral crystal field splitting diagram and fill this with electrons. Look where the
hs/ls possibilities are.

Solution: d4, d5, d6, d7.

EXERCISE 4.2
Exercise: Calculate, in units of o, the CFSEs of the following high-spin ions in their octahedral
complexes:
a) Fe2+ b) Mn2+ c) Mn3+ d) Co2+

Given: Octahedral complexes of Fe2+, Mn2+, Mn3+, Co2+.

Complexes are high-spin.

Needed: CFSEs in units o.

Strategy: Draw the octahedral crystal field splitting diagram.

Determine how much the t2g-level decreases and how much the eg-level increases with
respect to the reference level (Barycentre).
Fill in the correct number of electrons (taking into account that the complexes are high
spin). Calculate the CFSE.

Solution: All complexes hs.

Fe2+, d6, CFSE = 0.4o Mn2+, d5, CFSE = 0o
Mn3+, d4, CFSE = 0.6o Co2+, d7, CFSE = 0.8o

EXERCISE 4.3
Exercise: Predict the oxidation number of the central metal atom, the magnetic properties and the
CFSE for each of the following octahedral complexes:

(a) [Fe(CN)6]3- (b) [Ru(NH3)6]2+ (c) [Co(NH3)6]3+

(d) [PtCl6]2- (e) [Fe(H2O)6]2+ (f) [Mn(H2O)6]2+
(g) [CoF6]3- (h) [Cr(H2O)6]2+ (i) [Fe(CN)6]4-
(j) [Fe(H2O)6]3+ (k) [Cr(NH3)6]3+ (l) [Ru(NH3)6]3+

Given: A series of complex ions of transition metals.

Needed: The oxidation state of the central metal.

The magnetic properties of the ion.
The CFSE of the ion.

Strategy: Think of what the definition of the oxidation number is.

Determine the oxidation number of the metal.
Determine the number of d-electrons.
Draw the crystal field splitting diagram.
Determine whether the complex is hs or ls.
Fill in the correct number of electrons.

50
 Determine the type of magnetism based on the presence or absence of unpaired electrons.
Calculate the CFSE.

Solution: a) [Fe(CN)6]3-: CN- strong field ligand, so low spin; Fe(III), d5, t2g5; 1 unpaired electron,
paramagnetic; CFSE = 5∙0.4o - 2P = 2.0o - 2P
b) [Ru(NH3)6]2+: Ru 2nd row element, o large, so low spin; Ru(II), d6, t2g6, 0 unpaired
electrons, diamagnetic; CFSE = 6∙0.4o - 2P = 2.4o - 2P
c) [Co(NH3)6]3+: almost all Co(III) compounds low spin; Co(III), d6, t2g6, 0 unpaired electrons,
diamagnetic; CFSE = 6∙0.4o - 2P = 2.4o - 2P
d) [PtCl6]2-: Pt(IV), d6, low spin, diamagnetic; CFSE = 2.4o - 2P
e) [Fe(H2O)6]2+: H2O is a medium strong ligand, so high spin; Fe(II), d6, t2g4eg2, 4 unpaired
electrons, paramagnetic; CFSE = 0.4o
f) [Mn(H2O)6]2+: H2O is a medium strong ligand, so high spin; Mn(II), d5, t2g3eg2, 5 unpaired
electrons, paramagnetic; CFSE = 0o
g) [CoF6]3-: F- is a weak ligand, so high spin; Co(III), d6, t2g4eg2, 4 unpaired electrons,
paramagnetic; CFSE = 0.4o
h) [Cr(H2O)6]2+: H2O is a medium strong ligand, so high spin; Cr(II), d4, t2g3eg1, 4 unpaired
electrons, paramagnetic: CFSE = 0.6o
i) [Fe(CN)6]4-: Fe(II), d6, low spin, 0 unpaired electrons, diamagnetic; CFSE = 2.4o - 2P
j) [Fe(H2O)6]3+: Fe(III), d5, high spin, 5 unpaired electrons, paramagnetic; CFSE = 0o
k) [Cr(NH3)6]3+: Cr(III), d3, 3 unpaired electrons, paramagnetic; CFSE = 1.2o
l) [Ru(NH3)6]3+: Ru(III), d5, low spin, 1 unpaired electron; paramagnetic; CFSE = 2.0o - 2P

EXERCISE 4.4
Exercise: Is the complex [Co(H2O)6]2+ para or diamagnetic?
Determine the oxidation state of the central atom, the total number of d-electrons and the
number of unpaired electrons.
Calculate the Crystal Field Stabilisation Energy for the complex.

Given: An octahedral complex. Co is a 1st row element. H2O is a medium strong ligand.

Needed: The type of magnetism.

The oxidation number of the central metal.
The total number of d-electrons of the central metal.
The number of unpaired electrons.
The CFSE for the octahedral complex.

Strategy: Think of what the definition of oxidation number is.

Determine the oxidation number of the metal.
Determine the number of d-electrons.
Draw the crystal field splitting diagram.
Determine whether the complex is hs or ls.
Fill in the correct number of electrons.
Determine the type of magnetism based on the presence or absence of unpaired electrons.
Calculate the CFSE.

Solution: complex/ion oxidation number d-electrons unpaired elect. magnetism CFSE

[Co(H2O)6]2+ Co(II) 7 (hs) 3 paramagnetic 0.8o

EXERCISE 4.5
Exercise: a) Argue using crystal field theory that [Co(CN)6]3- is much more stable than [Co(CN)6]4-.
b) The complex [Co(NH3)6]3+ is orange-yellow, [CoF6]3- is blue. Explain qualitatively the
difference.
c) How should the crystal field splitting diagram be changed from [Co(NH3)6]3+ to obtain the
one for [Co(NH3)5F]2+, taking into account the fact that NH3 and F- have different ligand
strengths?
Note that the z-axis of the complex should go through the F-atom.

51
Given: a) [Co(CN)6]3- is much more stable than [Co(CN)6]4-.
b) [Co(NH3)6]3+ is orange-yellow, [CoF6]3- is blue.
c) [Co(NH3)5F]2+.

Needed: a) Explain the difference in stability.

b) Explain qualitatively the difference in colour.
c) Give the crystal field splitting diagram starting with the one for [Co(NH3)6]3+ (choose
the z-axis through the F-atom).

Strategy: a) The stability difference is linked to the difference in electron configuration.

Draw the CF diagram.
Determine the number of d-electrons.
Determine whether the complex ion is ls or hs.
Fill in the d-electrons in the diagram.
b) The colour difference is linked to the crystal field splitting parameter (o).
c) Determine the geometry of [Co(NH3)6]3+.
Draw the CF diagram.
Determine whether the strength of the field for NH3 is larger or smaller than that of F-.
Determine what the influence is of the difference in field strength on the CF diagram.
Fill in the d-electrons in the diagram, taking into account the hs/ls and the correct
number of d-electrons.

Solution: a) Cobalt has electron configuration 4s23d7 in the outer shell. In [Co(CN)6]3- the formal
oxidation number of cobalt is III; the electron configuration is then: 3d6 (the electrons in the
4s are first removed). In [Co(CN)6]4- the formal oxidation number of cobalt is II. The electron
configuration is then: 3d7 (The electrons in the 4s are first removed). CN- is a ligand with a
strong field, and the complexes are low spin. The CF diagrams for the two octahedral
complexes are:

For Co(III) only the lowest level is completely filled with electrons, which causes extra
stabilization compared to CO(II) because the seventh electron in CO(II) has to occupy the
higher energy level which will destabilize the complex.

b) [Co(NH3)6]3+ is orange-yellow and thus absorbs blue-violet (the complementary colour).

[CoF6]3- is blue and absorbs orange (the complementary colour).
The wavenumber of blue-violet is higher than that of orange. The energy difference
between the ground state and the excited state (the crystal field splitting in this case) will
be larger for [Co(NH3)6]3+ than for [CoF6]3-. So NH3 has a stronger field than F-.

c) NH3 has a stronger field than F-. In [Co(NH3)5F]2+, the dz² will be energetically more
favourable than in [Co(NH3)6]3+. The dx²-y² goes up in energy, if the centre of gravity rule is
applied. Also the other orbitals with a z-component (dxz and dyz) are lowered, while the dxy
rises. The CF diagrams are:

52
 The experimentally observed situation for [Co(NH3)5F]2+ is low spin.

EXERCISE 4.6
Exercise: Predict the relative positions of the absorption maximum in the UV/Vis-spectra of

a) [Ti(CN)6]3- b) [TiCl6]3- c) [Ti(H2O)6]3+.

Given: [Ti(CN)6]3-, [TiCl6]3- and [Ti(H2O)6]3+.

Needed: Relative position of absorption maximum in the UV/Vis-spectra.

Strategy: The transitions in the UV/Vis-spectra are caused by the d-d-transitions. The position of the
maximum is thus dependent on the strength of the ligand field. In the case of a d1 this
relation is linear. Determine the strength of the ligands (using the spectrochemical series).

Solution: Based on the spectrochemical series o(Cl-) < o(H2O) < o(CN-).
o = h = hc/. (Cl-) < (H2O) < (CN-); (Cl-) > (H2O) > (CN-).

EXERCISE 4.7
Exercise: A certain transition-metal ion forms two octahedral complexes from two different ligands,
one whose solution is red and the other blue. Using simple crystal-field theory, explain
which complex would be expected to arise from ligands that create the stronger field.

Given: Two octahedral complexes of the same metal, respectively red and blue.

Needed: Which ligands have the strongest crystal field.

Strategy: The colour of the substance is the complementary colour of the colour that is absorbed.
Determine the corresponding complementary colours.
Find the wavenumber of the complementary colour; this scales linearly with frequency, and
so with E (= h) = o.

Solution: Colour: red blue

complementary colour: green orange

o(red) > o(blue)

Extra: (nm): 530 620

(cm-1): 18900 16100

53
EXERCISE 4.8
Exercise: The ions [Mn(H2O)6]2+ and [Mn(CN)6]4- differ in colour and magnetic properties. Draw
energy-level diagrams illustrating the differences in crystal-field splitting of the d-orbitals for
the two ions and the distribution of electrons between the orbitals. Why do the ions have
different magnetic properties? Which ion would you predict to absorb visible radiation of
higher frequency?

Given: [Mn(H2O)6]2+ and [Mn(CN)6]4- differ in colour and magnetic properties.

Needed: Draw the CF diagram.

Fill in the d-electrons.
Explain the difference in magnetism.
Which of both complexes absorbs radiation with the highest frequency?

Strategy: Determine the geometry.

Draw the CF scheme.
Determine the d-electrons.
Determine whether the crystal field is strong or weak.
Fill in the d-electrons in the CF diagram, taking into account the strength of the field.
The difference in magnetism can be seen in the diagram.
From the strength of the field it can be deduced, using o = E = h, which of the ions
absorbs radiation with the highest .

Solution: Mn(II) 3d5

H2O complex: o < P; (P  25500 cm-1;   7800 cm-1); colourless
CN-: absorption around 26000 cm-1. violet (384 nm) complementary colour: yellow-green;
o > P
 = c/: (H2O) < (CN-)

EXERCISE 4.9
Exercise: Wilkinson’s catalyst [RhCl(PPh3)3] is used for the hydrogenation of alkenes. The catalytic
cycle for the hydrogenation of terminal alkenes is shown in the figure. Give for every
compound A, B, C, D, E and F the coordination number of the metal, the total number of
electrons in the valence shell of the metal and the oxidation number of the metal. Give for
every step in the catalytic cycle the name of the specific reaction type. How could you
summarize steps B-C-D?

54
Given: Catalytic reaction cycle for the hydrogenation of alkenes.

Needed: The coordination number of the metal.

The total number of electrons in the valence shell of the metal.
The oxidation number of the metal.
For every step in the catalytic cycle the specific reaction type.

Strategy: Count for every compound A-F the number of ligands, determine the charges of the ligands
and the oxidation number of the metal and apply the donor-pair method. Analyse the
reactions in terms of ligand association, ligand dissociation, oxidative addition, reductive
elimination, migratory insertion and α/β-elimination reactions. Check that the changes of
the coordination number, total electron count and oxidation number are in agreement with
the reaction types.

Solution: Coordination number Total electron count Oxidation number metal

A 4 16 I
B 6 18 III
C 5 16 III
D 6 18 III
E 5 16 III
F 6 18 III

A-B: oxidative addition, B-C: ligand dissociation, C-D: ligand association, D-E: 1,2-migratory
insertion, E-F: ligand association, F-A: reductive elimination. B-C-D: the combination of steps
B-C and C-D can be summarized as a dissociative ligand substitution reaction.

EXERCISE 4.10
Exercise: Which molecules from the following list should possess a permanent dipole moment?

a) CHCl3 b) SO42- c) 1,3,5-trinitrobenzene d) SO2 e) CO2 f) C2H2

Given: CHCl3, SO42-, 1,3,5-trinitrobenzene, SO2, CO2, C2H2.

55
Needed: Which molecules have a permanent dipole moment?

Strategy: Determine the Lewis structure and the geometry of the molecule/ion.
Determine whether the bond-dipole moments cancel each other out: if not, the molecule
has a permanent dipole moment.

Solution: CHCl3 and SO2. In all other compounds, the individual bond-dipole moments cancel each
other out.

EXERCISE 4.11
Exercise: The ClF3 molecule is polar, which structure does it have?

Given: ClF3 is polar.

Needed: Structure of the compound.

Strategy: Determine the possible Lewis structures and select those where the bond-dipole moments
do not cancel out.

Solution: A tbp electron pair geometry with two lone pairs. Because the molecule
is polar, the lone pairs should be in the equatorial plane. This is to be
expected based on the VSEPR rules. Structure: a t-shape.

EXERCISE 4.12
Exercise: Methyl-2-hydroxybenzoaat (methyl salicylate) and methyl-4-hydroxybenzoate both have
the same gross formula: HOC6H4COOCH3. The first compound has a melting point of -8oC,
while the second has a melting point of 127oC.
How can this large difference in melting points be explained?

Given: Methyl-2-hydroxybenzoate (methylsalicylate), melting point -8oC.

Methyl-4-hydroxybenzoate; melting point 127oC.
Formula of both: HOC6H4COOCH3.

Needed: Explain the difference in melting point.

Strategy: The formula is the same, so the difference should be in the spatial structure.
Draw these structures and find the differences.

Solution: Both molecules are capable of H-bonding, but in 2-hydroxybenzoate, this H-bonding is
intramolecular (left figure), in methyl-4-hydroxybenzoate this H-bonding is intermolecular
(right figure). The latter compound therefore has a higher melting point.

EXERCISE 4.13
Exercise: Formic acid, HCOOH, forms a dimer in the vapour phase. Deduce a reasonable structure
based on hydrogen bonds between the formic-acid molecules.

56
Given: HCOOH is a dimer in the gas phase. As a dimer, it can form hydrogen bonds.

Needed: The structure of the dimer.

Strategy: Draw the structure, assuming it contains hydrogen bonds.

Solution:

EXERCISE 4.14
Exercise Why are intermolecular attractions so strong in liquids and solids, but so weak in gases?

Given: Intermolecular forces are strong in solids and liquids, but weak in gasses.

Needed: Why is this the case?

Strategy: Determine which parameters influence the intermolecular forces.

Determine which of these parameters are different for liquids and solids compared to
gasses.

Solution: The forces are proportional to r-6; In gases, the distance between molecules is larger than
in liquids.

EXERCISE 4.15
Exercise What type(s) of intermolecular attractive forces are found in the following compounds?

a) HCl b) Ar c) CH4 d) HF
e) NO f) CO2 g) H2S h) SO2.

Given: A number of molecular formulas.

Needed: Indicate which type of intermolecular forces (between multiple molecules of the mentioned
compound/atoms) are present.

Strategy: Give the definition of each of the intermolecular forces and determine which are applicable
on these molecules.

Solution: Keesom force Debye force London force H-bonds

HCl x x x
Ar x
CH4 x
HF x x x x
NO x x x
CO2 x
H2S x x x
SO2 x x x

Keesom force: permanent dipole - permanent dipole interactions

Debye force: permanent dipole - induced dipole interactions
London force: induced dipole - induced dipole interactions
H-bond: electrostatic force of attraction between a hydrogen (H) atom which is
covalently bound to a more electronegative "donor" atom, and
another electronegative atom bearing a lone pair of electrons (the
hydrogen bond acceptor)

57
INFORMATION ACCOMPANYING THE COMPUTER MODULE

Introduction/background

During the course you will learn how to qualitatively construct an MO diagram. This means
you should use approximations when combining AOs to MOs. AOs that are close to each
other in terms of energy (rule of thumb: a difference less than 15 eV) can interfere, but to
what extend and what the exact effect is, can only be roughly estimated. Furthermore, you
will learn that bonds in molecules can be described localized (using hybridization) or
delocalized (using Symmetry Adapted Linear Combinations of AOs, SALCs). For diatomic
molecules this is less relevant, but for more complex molecules this leads to large differences
in both the approach and results. A nice example is methane, and this molecule is also
covered in the computer module.

You are used to work towards the MOs starting from the AOs. The result is a qualitative MO
diagram where the position of the energy levels can approximately be determined. It is
however important to be able to explain how MOs were formed from AOs and how certain
properties of the molecules, like the position of the energy levels, can be understood based
on the orbitals shown.

In the computer module you will, by analyzing MOs of molecules, reason backwards in order
to determine from the energy levels and the information of the molecule, the origin of the MO
diagram. Here, several aspects, such as orbital energy, bondorder, bonding MO, non-
bonding MO, anti-bonding MO, HOMO, LUMO, para and diamagnetism, s-p orbital mixing,
and others terms are covered.
Understanding the various orbitals you see will of course require some exercise. In the
beginning, simple molecules will be covered, and the complexity will gradually increase.

Calculations on molecules

When constructing an MO diagram with SALCs you use descriptions of a molecule based on
delocalized bonds. How do you normally construct these with pen and paper?

1] Determine the structure of the compound:

- determine the electron configuration of the atoms.

- draw the Lewis structure.
- apply VSEPR theory.

2] Determine which valence AOs (of the peripheral or central atoms) are energetically suited
for overlap.

3] Find the combinations of AOs (SALCs) of the peripheral atoms that can have positive
overlap with the AOs of the central atom.

4] Determine if the number of SALCs found is equal to the number of AOs of the peripheral
atoms.

- if it is less, add non-bonding SALCs.

- if it is more, find the identical SALCs.

5] Combine the SALCs with the AOs of the central atom to obtain MOs (bonding scheme).

58
6] Determine whether the number of MOs is the same as the total number of initial orbitals
(AOs and SALCs)

7] Determine the type of symmetry of the bonds ( or ).

8] Draw the MO diagram.

9] Fill in the correct number of electrons in the MO diagram and determine the bondorder.

If you perform molecular calculations you use a delocalized approach. All AOs enter the
calculation separately and hybridization, which is essentially pre-processing of AOs, is not
needed. Hybrids are therefore not encountered in the examples you will see. For the
molecules you will find in the computer module, the MOs and energy levels have already
been calculated, using an approach similar to the one illustrated above. In these calculations,
as few approximations as possible were used, leading to a much more accurate MO diagram
– in terms of the position of the energy levels and the interference of MOs – than when
constructed using pen and paper. Furthermore, the calculations have led to a three-
dimensional image of the MOs which can be viewed on the computer. The calculations for
the example molecules have already been completed, and the result can be viewed, and you
can determine the properties of the molecules.

In the computer module, you will find the following molecules to work with:

H2, C2, N2, O2, F2, HF, CO, CH4, NH3, H2O, C2H2, C2H4, CH2O, C3H4.

Goal of the computer module

After finishing the computer module:

- You will have a better feeling for the shape of orbitals and their orientation relative to
the atomic nuclei.
- You will be able to name the type of MOs (, , *, *, bonding, non-bonding, anti-
bonding) by using the MO diagram and visualization of the MOs.
- You can indicate what the HOMO and LUMO are.
- You can determine the bondorder using an MO diagram and the orientation and
shape of the orbitals.
- You can recognize from an MO which AOs contributed to the MO.
- You can, taking into account the position of the energy levels, determine whether a
molecule is para- or diamagnetic.
- You can determine whether there is s-p orbital mixing based on the shape of the MO
and the position of the energy levels.
- You can recognize the nodes in an MO.
- You understand the effect of a polarity difference on the shape and orientation of a
MO.
- You can indicate which MOs in a molecule are delocalized.

59
INSTRUCTION

The Quiz

During the computer module you will answer a series of multiple-choice questions. Each
question covers a specific aspect of a certain molecule. To answer the questions you can
open a window where you can view the MO diagram, the AOs, and the MOs of the molecule.
This window is a tool which helps you answer the questions correctly.
After answering all the questions your score will be calculated and saved. You can determine
which questions were wrongly answered, and you will be provided with an explanation about
the question. It is also possible to take the test a second time. Your score does not count
towards your final grade!
It is advised to also write down your answers to the questions on paper. That way you can
compare your answer to those of other students at the end of the module.

Visualizing Orbitals

If you study a molecule from the series more closely, for every energy level in the MO
diagram you will be able to look at a “Molecular Orbital” in a three-dimensional representation
by clicking on the corresponding bar using the computer mouse.
It is also possible to look at the “Atomic Orbitals” that could possibly have been combined
into the MOs by clicking on them in the same way as described before.

Pen and paper as a tool

To get a better overview you should work as follows for each molecule:

- Redraw the MO levels on paper (on the middle of the page);

- Put the AOs or SALCs that are relevant for construction of the MO to the sides of
those MOs (See Appendix 3.1 for constructing an MO diagram with SALCs; for the
energies of the AOs you can study Appendix 3.2).

- Draw lines from the AOs or SALCs to the MOs if there is a relation; to establish this,
look at the MOs, determine their bond type and then reason backwards.

- Fill in all available electrons in the MO diagram.

60
APPENDICES

Appendix 1.1

General information and physical constants

Atomic mass unit u 1.66054∙10-27 kg

Atom radius H-atom (according to Bohr) ao = 4εoħ2/mee2 5.29177∙10-11 m
Avogadro’s constant NA 6.02214∙1023 mol-1
Boltzmann’s constant k 1.38066∙10-23 J K-1
Faraday’s constant F = eNA 9.6485∙104 C mol-1
Planck’s constant h 6.62608∙10-34 J s
Reduced Planck’s constant ħ = h/2 1.05457∙10-34 J s
Rydberg’s constant (heavy atoms) R∞ = mee4/8h3cεo2 1.09737∙107 m-1
Rydberg’s constant (hydrogen) RH = µe4/8h3cεo2 1.09677∙107 m-1
Dielectric constant in vacuum εo= 1/c2µo 8.85419∙10-12 J-1 C2 m-1
Elementary charge e 1.602177∙10-19 C
Gas constant R = kNA 8.31451 J K-1 mol-1
8.20578∙10-2 dm3 atm K-1 mol-1
Electron mass me 9.10939∙10-31 kg
Proton mass mp 1.67262∙10-27 kg
Neutron mass mn 1.67493∙10-27 kg
Vacuum permeability µo 4∙10-7 J s2 C-2 m-1
Speed of light c 2.99792458∙108 m s-1

Appendix 1.2

The atom through the ages

Democritus (~460-370 B.C.): small, indivisible particles: atoms

John Dalton (1766-1844): different characteristic weights; solid, uniform particle
J.J. Thompson (1856-1940): discovers the electron: sponge-like atom (raisins in a
pudding)
Ernest Rutherford (1871-1937): atom is mostly empty space! Planetary model.
Niels Bohr (1885-1962): electrons occupy only certain orbits; energies are quantized
Quantum Mechanics (1920-1930): electrons behave like waves: orbitals!

Appendix 1.3
A few important formulas

c =  : the speed of light is equal to the frequency times the wavelength of photons.

c is the speed of light (2.99792458∙108 m s-1)

 is the frequency of the radiation
 is the wavelength

Planck: E = nh : the transfer of energy in a system is quantized.

E is the change in energy

n is an integer
h is Planck’s constant (6.62608∙10-34 J s)
 is the frequency of the radiation

61
Einstein: E = h : electromagnetic radiation consists of particles: photons; frequency of the
photon determines the energy.

E is the energy of the photon

h is Planck’s constant (6.62608∙10-34 J s)
 is the frequency of the radiation

De Broglie:  = h/p : a particle can be described as a wave; momentum of the particle

determines the wavelength.

 is the wavelength
p is the momentum (= mv, m = mass, v = speed)

Rydberg: 1/ = Z2R(1/n12 - 1/n22) : describes emission spectra of hydrogen-like atoms.

 is the wavelength
Z is the nuclear charge/atomic number
R is Rydberg’s constant (1.09737∙107 m-1)
n1 and n2 are integers

From this, and Bohr, we can find for the orbital energy: E = -Z2Rhc/n2 (hydrogen-like)

Particle in:  = 2a/n : the possible wavelengths and energies of the particle are
a box E = n2h2/8ma2 determined by the size of the box.

 is the wavelength
a is the size of the box
n is an integer
E is the energy of the particle
h is Planck´s constant (6.62608∙10-34 J s)
m is the mass of the particle

Extra: E = mc2 : as we all know!

According to De Broglie there is a relation between the wavelength and the momentum of a particle:
 = h/mv. Einstein showed that the energy of a photon is related to the wavelength of the photon:
E = hc/. The speed of the photon is c. Substituting h/mc for  in the formula E = hc/ yields:

E = hcmc/h = mc2

Appendix 1.4
Converting from eV to J; energy as a wavenumber

Definition of electron volt ( =eV): charge of an electron moved over a charge difference of 1 Volt. First
compare the dimensions of eV (CV) and J (CV). J and eV are both measures of energy.

An electron volt is the charge of 1 electron (= 1.602∙10-19 C) over a charge difference of 1 Volt.
J = VC. So 1 eV = 1.602∙10-19 C ∙ 1V = 1.602∙10-19 J.

Energy can also be represented as a wavenumber (1/) which is given in the unit cm-1 (reciprocal
centimeters). By dividing the energy by hc (which converts E = h to 1/) and subsequently
representing  in cm you acquire a (non-SI) unit for energy.

E(eV) = hc/  1/ = (1.602∙10-19 J) / (6.626∙10-34J s∙2.998∙1010 cm s-1) = 8065.5 cm-1

So, a wave with a wavenumber of 8065.5 cm−1 will have a photon energy of 1eV (or 1.602∙10-19 J).

62
Appendix 1.5
The difference between the functions R(r), R(r)2 and r2R(r)2

All three functions are radius dependent. R(r) is the radial part of the wave function, whose solutions
obtained from the Schrödinger equation give the energy (an eigenfunction) for the radial part R(r).
R(r)2 describes the probability to find an electron at a distance r from the nucleus. (dimension:
1/volume). r2R(r)2 is the density distribution function that describes the electron density in a small layer
between r and r + dr (dimension: 1/length).

Appendix 1.6

The number of nodes in wave functions

Total number of nodes in an orbital =n-1

Number of nodes in the angular part =l
Number of nodes in the radial part =n-l-1

Example: The number of radial and angular nodes in the wave functions corresponding to the
following orbitals: 1s, 3s, 3d, 2p and 3p.

Solution: l Radial nodes Angular nodes Total number of nodes

n-l-1 l n-1
1s 0 0 0 0
3s 0 2 0 2
3d 2 0 2 2
2p 1 0 1 1
3p 1 1 1 2

Appendix 1.7

The relation between the quantum numbers

n = principal quantum number

l = orbital angular momentum quantum number (or orbital quantum number)
ml = magnetic quantum number
ms = spin magnetic quantum number (or spin quantum number)

n = 1, 2, 3, ……., infinity
l = 0, 1, 2, ……, n-1
ml = -l, -l+1, …., 0, ….., l-1, l
ms = ½ or -½

63
Appendix 2.1

The Periodic Table of the Elements

Appendix 2.2
Electron configuration of atoms compared to ions

The way in which orbitals of the elements are filled with electrons roughly follows the following
diagram:

1s

2s 2p

3s 3p 3d

4s 4p 4d 4f

5s 5p 5d 5f 5g

6s 6p 6d 6f

There are exceptions! For example the electron configurations of Cr, Cu and La.

For positively charged transition metals, the s-electrons first have to “move” to the d-orbitals before the
electrons are removed to acquire the correct charge.

For reactivity, only the valence-electron configuration of the elements and ions is important.

64
Appendix 2.3

Trends in atomic radii and ionisation energy

Atomic radii versus Z (atomic number).

First ionisation energy versus Z (atomic number).

65
Appendix 2.4
Strategy for the construction of Lewis structures

[1] Determine the atomic sequence.

[2] Count the total number of available electrons in the valence shells.
[3] Place an electron pair in each bond.
[4] Give the peripheral atoms as many electrons as needed to reach the noble gas configuration.
[5] Put the remaining electrons in pairs on the non-peripheral atoms.
[6] Complete, if needed, the octet on the non-peripheral atoms by formation of double or triple bonds.
[7] Minimize, by shuffling electron pairs, the formal charge: as little charge as possible, if possible no
multiple charges and no equal signed charges next to each other.
[8] Note that exceeding the octet rule may not occur for C, N, O and F.

A pair of electrons can be indicated as a pair of dots or as a

dash. The three Lewis structures for O2 on the right therefore
describe the same Lewis structure. In this study guide, and
also in the IC and OC text books, lone pairs are indicated by
a pair of dots while bonding electron pairs are indicated by a
dash (as for the O2 Lewis structure in the middle).

Appendix 2.5

Definition of formal charge

The formal charge on an atom is defined as the charge that an atom in a molecule would have when
all atoms would have the same electronegativity, so when there would be 100% covalence.

Note that the formal charge isn’t the true charge of an atom!

The formal charge (FC) can be calculated using the formula: FC = N - NLP - ½NBP
Where N is the number of valence electrons of the neutral atom, NLP is the number of electrons that
resides in lone pairs and NBP is the number of electrons that resides in bonding pairs.

Appendix 2.6

Definition of formal oxidation state (oxidation number)

The formal oxidation state of an atom is defined as the charge that an atom in a molecule would have
if the atom would be fully ionized.

For the determination of the formal oxidation state of the atoms in a molecule/ion, first place the
available electron pairs on the most electronegative atoms until they obey the octet rule. Afterwards,
the formal oxidation state can be determined per atom.

Note that the formal oxidation state isn’t the true charge of an atom!

Appendix 2.7

Validity of the octet rule

The octet rule is only completely valid for the elements C, N, O and F. Violation of the octet rule
(exceeding the octet) may not occur for these elements. H satisfies the duet rule, while other elements
may exhibit valence shell expansion or can lead to bonds with less than two electrons.
For non-exotic compounds, the octet rule is a nice rule of thumb.

66
Appendix 2.8

Electron pair arrangement and molecular geometry

67
Appendix 3.1

Strategy for the construction of an MO diagram

Description using localized bonds

Determine the structure of the compound.

From this, determine the hybridization type.

Determine which AOs of the atoms, that are not used in hybrids, are energetically suited for overlap.

Determine whether the total number of orbitals (hybrid + other orbitals) is equal to the initial number of
orbitals.

Determine which hybrid-orbitals are suited for bonding in terms of symmetry.

Combine the hybrid-orbitals with the AOs or the hybrids of the peripheral atoms (bonding scheme).

Combine, if possible, the remaining AOs with those of the peripheral atoms.

Determine if the number of MOs that was found, is equal to the initial number of orbitals:
 If it is less, check if non-bonding MOs have been forgotten.
 If it is more, check the diagram with respect to the validity of the combinations.

Determine the type of symmetry of the bonds (σ or π).

Draw the MO diagram.

Count whether or not the number of MOs is equal to the initial number of orbitals.

Fill in the right number of electrons in the MO diagram and determine the bondorder.

Description using delocalized bonds

Determine the structure of the compound.

Determine which AOs of the central atom, and which of the peripheral atoms, are suited for overlap.

Find, for every AO of the central atom, the combination of AOs that can give positive overlap (SALCs).

Determine whether the number of SALCs is equal to the total number of AOs of the peripheral atoms:
 If it is less, add non-bonding SALCs.
 If it is more, find the identical SALCs.

Combine the SALCs with the AOs of the central atom (bonding scheme).

Determine whether the number of MOs is equal to the initial number of orbitals (AOs and SALCs).

Determine the type of symmetry of the bonds.

Draw the MO diagram.

Count whether the number of MOs is equal to the number of AOs.

Fill in the correct number of electrons in the MO diagram and determine the bondorder.

68
Appendix 3.2

Estimation of a few atomic orbital energies (eV)

Li Be B C N O F Ne
2s -6 -10 -15 -20 -28 -33 -40 -48
2p -9 -13 -15 -18 -20 -23

Note that the 1s of H has an energy of -13.6 eV

As a rule of thumb it can be assumed that orbitals that differ less than 15 eV in energy will surely
interfere (if the orbital symmetries are compatible).

69
Appendix 4.1

Crystal Field Stabilisation Energy for an octahedral complex

d-electron state CFSE1,2 state CFSE1,2

configuration
o < P o > P
d1 t2g1 0.4 o
d2 t2g2 0.8 o
d3 t2g3 1.2 o
d4 t2g3eg1 (hs) 0.6 o t2g4 (ls) 1.6 o - P
d5 t2g3 eg2 (hs) 0 o t2g5 (ls) 2.0 o - 2P
d6 t2g4 eg2 (hs) 0.4 o t2g6 (ls) 2.4 o -2P
d7 t2g5 eg2 (hs) 0.8 o t2g6 eg1 (ls) 1.8 o - P
d8 t2g6 eg2 1.2 o
d9 t2g6 eg3 0.6 o
d10 t2g6 eg4 0 o

1 The indicated energy is the (absolute) value by which the energy lowers in regard to the reference
level (the energy of d-orbitals in a spherically shaped charge field). In some books de CFSE has a
negative sign (one could then talk about Crystal Field energy): the reference level has the energy
value 0, the specific configuration then has a lower, thus negative energy.

2 Please take note: the number of times the spin pairing energy is taken into account is also calculated
with respect to the reference level!

Appendix 4.2

Octahedral complexes: low spin or high spin?

bi- and trivalent first row transition-metal complexes:

Always high spin (hs), unless:

-they have CN-, PR3 or CO as ligands: low spin (ls).
-it concerns Co(III): low spin, unless F- is the ligand.

Second and third row transition-metal complexes:

Always low spin (ls).

Appendix 4.3

Tetrahedral and square planar complexes

Square planar complexes are found in the first row d8 metals with a strong ligand (CN-, PR3 or CO)
and for d8 metals from the second or third row transition metals.
In other cases one will find tetrahedral complexes.

Note that tetrahedral complexes are always high spin (hs)!

70
Appendix 4.4
Total electron count metal (donor-pair method)

The total electron count on the metal (valence shell of the metal) is the sum of the electrons the metal
provides and the electrons provided by the ligands (most ligands: 2 each).

How to determine the total electron count using the donor-pair method?

-look at the net charge of the complex

-determine the oxidation number of the metal; note that in general the electronegativity of the metal is
smaller than the electronegativity of the ligands
-determine the d-electron configuration of the metal (see Appendix 2.2)
-electrons in the d-orbitals of the metal = number of electrons the metal provides
-count the number of electrons provided by the ligands

Total electron count = electrons provided by the metal + electrons provided by the ligands.

Note: d-block metals try to fill their ns, np and (n-1)d orbitals with their own d-electrons and the
electrons provided by the ligands: 18 electron rule.

Appendix 4.5
Intermolecular interactions

Introduction
Without the existence of intermolecular interactions, the forces between molecules, it cannot be
explained that compounds can be liquid or solid. In compounds that consist of ionic lattices, the
distinction between intramolecular (interactions within a molecule) and intermolecular interactions has
no meaning. In a lattice of NaCl, each Na+ ion is surrounded by six Cl- ions and each Cl- ion by six Na+
ions. Inter and intramolecular cannot be separated in ionic compounds.
The intermolecular forces in non-ionic compounds are caused by electrostatic interaction of permanent
dipoles on each other, permanent dipoles on induced dipoles and/or induced dipoles on each other.
Intermolecular forces are often weak compared to intramolecular forces. As an example: H2 has a
melting point of -259°C and a boiling point of -253°C, while at 2400°C only 1% of the molecules is split
into atoms.

Permanent electric dipoles

Two electric charges +q and -q, that have no common centre, but are separated by a distance r, form
a permanent electric dipole,  = qr. The dipole moment is a vector quantity, and thus has both size
and direction. The size is often presented in units of Debye: D = 3.4∙10-30 C m. The order of magnitude
is 0 to 10 D (for small molecules 0 to 2 D).
In chemistry, the direction of the dipole is defined as going from + to -. So, the dipole moment vector is
pointing from the positive charge to the negative charge. However, the opposite sign convention for
the dipole, from the negative charge to the positive charge, is used in physics!
A diatomic heteronuclear molecule always has a certain dipole. Generally, the most electronegative
atom is the negative end of the dipole, but there are exceptions, especially when anti-bonding orbitals
are occupied: the dipole moment of CO is very small and the negative end is at the C atom, while O is
the most electronegative atom!
For a molecule with multiple nuclei the molecular dipole moment is the result of the various bond
dipole moments. Whether or not a dipole is present says something about the structure. A molecule
with a dipole moment is asymmetric, while a molecule without one is symmetric: CO2 has no dipole
moment because it is linear; H2O and NO2 are non-linear molecules and do have a dipole moment;
COS is asymmetric and will have a dipole moment; BrF3, CH4, PF5 and SF6 have no dipole moment,
IF5 does have a dipole moment.
Some care is needed when comparing the magnitude of dipole moments: NH3 has a dipole moment of
1.48 D, NF3 of 0.2 D. Both compounds are asymmetric and trigonal pyramidal. In NH3 the H-N bond
polarizations and lone pair are additive while in NF3 the N-F bond polarizations and lone pair are
subtractive.

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Induced dipoles
If an atom or molecule without a permanent dipole (CH4 for example) is brought into an electric field, a
partial charge separation occurs: polarization. A dipole is induced. The extent to which this charge
separation occurs is proportional to the electric field. The proportionality constant  is called
polarizability. The dimension is J-1 C2 m2. Sometimes it is defined as ' = /4o which has the
dimension of a volume (generally expressed in cm3), which is why it is called polarizability volume (o
is the dielectric constant (permittivity) in vacuum; this is a fundamental constant with a value of
8.854∙10-12 C2 J-1 m-1). The larger the polarizability volume, the higher the polarizability.

Permanent dipole – permanent dipole interactions (Keesom force)

In a gas or liquid, in which the molecules have a permanent dipole, the total dipole moment would be
zero if all dipoles are oriented randomly. However, the dipoles do orient themselves towards each
other (+ to – and – to +) because of their interaction. The interaction is an attractive force and is
proportional to 1/r6. Full alignment is limited because of the movement caused by temperature.
For high temperatures, this alignment is lost. For permanent dipoles with a magnitude of 1 D (like HCl)
on a distance of 0.3 nm the interaction energy at 25oC is -1.4 kJ mol-1. Compare this to the bond
energy of HCl: -299 kJ mol-1.

Permanent dipole – induced dipole interactions (Debye force)

The interaction energy between a permanent dipole and an induced dipole is proportional to 2, ' and
r--6. The interaction isn’t temperature dependent, as the temperature induced movement can’t change
the direction of the induced dipole moment. The interaction energy for a permanent dipole of 1 D (as
for HCl) and a polarizability volume ' = 10-23 cm3 (as for benzene) on a distance of 0.3 nm of each
other is -0.8 kJ mol-1.

Induced dipole – induced dipole interactions (dispersion or London force)

Two molecules without permanent dipoles still interact. Benzene is a liquid, even though  = 0 and the
boiling point of Cl2, He and H2 isn’t 0 K.
This interaction is the induced dipole – induced dipole interaction. The electrons of an atom or
molecule constantly move around relative to the nuclei. Take for example H2: on average the electrons
are as close to one nucleus as to the other. On average, there is no dipole. At a certain point in time,
the electrons are more concentrated to either one of the nuclei: the centres of the positive and
negative charges no longer coincide and there is always a slight dipole. This dipole in turn induces a
dipole in a nearby molecule, and they start interacting. If the direction of the dipole of the first molecule
changes, then the induced dipole of the second molecule will as well. The magnitude of this
interaction, also called dispersion or London force, is proportional with the polarizability volume ' of
both molecules and with r-6. For two methane molecules ('= 2.6∙10-24 cm3 and r = 0.3 nm) the
interaction is: -4.7 kJ mol-1. This type of interaction also plays a role for molecules that have a
permanent dipole moment, however, measuring these interactions separately is impossible.

Van der Waals interactions

Of the three mentioned interactions, together called van der Waals interactions, the induced dipole –
induced dipole interaction is the most important, except for molecules with a small polarizability
volume and a large permanent dipole, like HF and H2O.
The van der Waals energy can in total be written as V(r) = -C6/r6, where C6 is a coefficient which is
dependent on the nature of the molecules. The complete expression of the intermolecular energy
should also contain a repulsive term. When the distance is especially short, the electrons will repel
each other, much like nuclei. This repulsive force increases rapidly in magnitude as soon as the
distance becomes smaller. The total interaction can be described using the Lennard-Jones equation:

V(r) = Cn/rn - C6/r6 with n = 9 - 12.

Generally, the so called (12,6) potential is used with n = 12.

If r is small, the repulsive term dominates, for large r, the attractive term dominates.
As the size of the atom increases, the van der Waals bond becomes stronger, which can be observed
in the boiling points:

He Ne Ar Kr Xe
rvdW (pm) 140 154 192 200 220
Boiling point (K) 4.2 27 87 121 165

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The hydrogen bond
In general, the interactions between permanent dipoles are small. An exception is the interaction that
occurs when hydrogen is bonded to a highly electronegative atom: F, O, N and to a lesser extend Cl.
The small H atom can get really close to the electronegative atom and can be strongly polarized. It
therefore induces a strong electrostatic attraction with an electronegative atom of a neighbouring
molecule. The strength of such a bond is 20-30 kJ mol-1 (covalent bonds are around 200 kJ mol-1).
These bonds are often linear. Such a surprisingly strong interaction is called a hydrogen bond.
Experimentally, the consequences of the presence of hydrogen bonds can be seen in the series of
boiling points of hydrides. The boiling points of the hydrides of group 14 elements increase with
increasing molecular mass, as is expected. For the hydrides of group 15, 16 and 17 the same rules
hold, with the exception of the first members of the series. The presence of hydrogen bonds is most
often seen as the explanation for this phenomenon. For the melting points of the hydrides the situation
is analogous: even now the melting points of H3N, H2O and HF are abnormally high compared to the
other hydrides in the group. The good mixability of lower alcohols and hydrocarbon acids with water is
explained by the formation of hydrogen bonds.

Other phenomena where hydrogen bonds play a role are: the dimer structure of acetic acid, the
structure of ice, the planar structure of nickeldimethylglyoximatocomplex and the spiral structure of
proteins and nucleic acids.
The simply electrostatic model explains both the relative bond energy and the geometry. Still, there
are reasons to assume that something more is going on than just a strong dipole–dipole interaction.
The short distances of the hydrogen bonds would imply a strong nucleus–nucleus repulsion. Except
using an electrostatic model, a description can be made using the MO model.

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