Chapter 18.1 Kognity

5/22/2018 Book | Kognity
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Subtopic 18.1
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Lewis theory of acids and
18.1 ()
bases
18.1.0 The big picture ()
18.1.0 ()
18.1.1 Lewis theory of acids and bases ()
18.1.1 () 18.1.2 Checklist ()
18.1.2 ()
The big picture

Essential idea: The acid–base concept can be extended to reactions that do not
involve proton transfer.
A fundamental reaction type

In section 8.1.1 (https://app.kognity.com/study/app/chemistry-hl-2016/acids-
bases/acid-base-theory/theory-of-acids-and-bases/), we saw an important type of
reaction defined in terms of proton (H+) transfer: acid–base reactions described in
terms of the Brønsted–Lowry theory – a category of reactions that pervades a great
deal of everyday life and whose associated language colours our everyday speech.
There is a broader definition of acid–base activity that covers a broader range of
chemical reactions: the theory that defines acid–base behaviour in terms of the
transfer of an electron pair, with the subsequent formation of a coordinate bond.
Reactions of this kind are called Lewis acid–base reactions after the American
chemist, G.N. Lewis, who first identified them and was later killed by them (he died
in his lab after ingesting cyanide ions, a poison that acts by this kind of reaction). We
could represent this type of reaction as A + :B → A–B, where the double dot on B
represents an electron pair that is shared with A as a coordinate covalent bond is
formed.

https://bssimprug.kognity.com/schoolstaff/app/chemistry-hl-2016/book/acids-bases-ahl/lewis-theory-acids-bases/the-big-picture/?source=Table%20of%20contents
One role of Lewis acid–base reactions is to bring colour to the world. Transition
metal complexes are often brightly coloured as the result of the binding of ligands
such as water molecules to the central metal ion by coordinate bonding. The
hemoglobin in our blood is another example, its red colour being due to the heme
complex involving iron. The oxygen carrier, hemoglobin, is a protein macromolecule
that has four iron(II) ions embedded in it (Figure 1). The bonds between the iron and
the protein are the consequence of Lewis acid–base interactions, with Fe2+ the
Lewis acid and each :N a Lewis base. When you breathe in this structure takes part in
a further Lewis acid–base reaction when oxygen molecules, acting as Lewis bases,
use a pair of electrons to form a bond to each Fe2+ ion in the hemoglobin molecule.
Figure 1. The structure of the heme group in hemoglobin showing the coordinate

bonds formed to the Fe2+ ion.
Once captured, the precious oxygen is transported in our bloodstream to be released

to take part in reactions in the tissues of the body (Figure 2).
Figure 2. A visual model of the oxygen-binding process, showing the remarkable

adjustment of the hemoglobin structure as it binds and then detaches oxygen.
Oxygen binds to all four Fe2+ ions (purple/pink spheres) simultaneously. The
hemoglobin molecule operates as an oxygen-carrying molecular 'machine'.
Suffocation by carbon monoxide (CO) poisoning is another Lewis acidbase reaction.

The carbon monoxide usurps oxygen's binding to the iron in hemoglobin, and binds
more strongly. Oxygen transport to the tissues is blocked, and as a result suffocation
takes place at a molecular level.
Lewis theory of acids and

bases
The Brønsted–Lowry theory of acids and bases was covered in section 8.1.1
(https://app.kognity.com/study/app/chemistry-hl-2016/acids-bases/acid-base-
theory/theory-of-acids-and-bases/). In this theory, acids and bases are defined in terms
of the transfer of protons (H+ ions). In 1932, a more general definition of acids and
bases was proposed by Gilbert Lewis. This defined acids and bases as either electron
pair acceptors or electron pair donors. The Lewis definition of acids and bases
is much broader and includes a whole range of reactions that do not involve the
transfer of protons.
 Important
A Lewis acid is an electron pair acceptor.

A Lewis base is an electron pair donor.
The electron-deficient compound boron trifluoride, BF3, is a good example of a

Lewis acid (Figure 1). It forms an adduct (the product of the addition of two
molecules) with ammonia, NH3, by forming a coordinate covalent bond. In this
reaction, BF3 is acting as a Lewis acid and NH3 as a Lewis base. The donor orbital on
the nitrogen atom of NH3 contains a lone pair of electrons and the acceptor is the
empty p orbital remaining after the sp2 hybridisation of boron in the BF3 molecule.
Figure 1. The formation of the adduct between ammonia and boron trifluoride;

NH3 is acting as a Lewis base and BF3 as a Lewis acid.
 Nature of Science
Theories can be supported, falsified or replaced by new theories – Lewis

theory serves to extend the Brønsted–Lowry theory of acid–base
behaviour
Early definitions of acidity associated this property with the presence in

a compound of a particular element, with such ideas culminating in the
Brønsted–Lowry theory. In contrast, the Lewis definition does not
attribute acidity to the presence of one particular element, but rather to
electronic arrangement and availability for bonding. The Lewis theory

does not falsify the Brønsted–Lowry theory but serves to extend it to a
wider range of compounds: Brønsted–Lowry acids and bases are
subsets of Lewis acids and bases respectively.
All Brønsted–Lowry acids are Lewis acids, and all Brønsted–Lowry bases
are Lewis bases. When a proton, H+, accepts a lone pair from the oxygen
atom in a water molecule forming an oxonium (or hydronium) ion, H3O+,
the H+ is acting as a Lewis acid and the water as a Lewis base.
A Brønsted–Lowry base is a particular example of a Lewis base that uses

a non-bonding pair of electrons to link specifically to a proton, as
opposed to any other ion or molecule.
Certain reactions that are not classified as acid–base reactions under the Brønsted–
Lowry theory can be classified as such under the Lewis definitions. Therefore, the
terms Lewis acid and Lewis base are often applied to species that are Lewis acids and
bases but not Brønsted–Lowry acids and bases.
 Exam Tip
Make sure that you can recognise species that act as Lewis acids; these
species are lone pair acceptors, and are a positively charged ion or have
a vacant orbital to accept a lone pair. In contrast, Lewis bases are species
that are a negatively charged ion or have a lone pair of electrons to
donate.
One interesting example of Lewis acid–base behaviour is shown by the aluminium

chloride dimer, Al2Cl6. This dimer is formed in the vapour phase when aluminium
chloride, AlCl3, sublimes. Each aluminium chloride molecule forms a coordinate
covalent bond to the aluminium atom of the other molecule using one of the lone
pairs of electrons on a chlorine atom, while simultaneously accepting a lone pair of
electrons from the chlorine atom of the other molecule (Figure 2). Each aluminium
chloride molecule is, therefore, acting as both a Lewis acid and a Lewis base at the
same time.
Figure 2. The formation of the Al2Cl6 molecule.
The complex ions formed by transition metals are structures showing further
examples of Lewis bonding (section 13.1.3
(https://app.kognity.com/study/app/chemistry-hl-2016/periodic-transition-metals-
ahl/properties-of-the-transition-elements/structure-of-complex-ions/)). In aqueous
solution, metal ions become surrounded by water molecules. In many examples, the
transition metal ions become surrounded by six water molecules; for example, the
Fe3+ ion exists as the hexaaquairon(III) ion, [Fe(H2O)6]3+, in solution (Figure 3).
Figure 3. The structure of the [Fe(H2O)6]3+ complex ion showing the water molecules
(ligands)
acting as Lewis bases.
In this complex, the six ligands each donate a lone pair of electrons from the oxygen
atoms of the water molecule to the empty 3d orbitals of the central iron(III) ion. The
water molecules are acting as Lewis bases (electron pair donors) and the iron(III) is
acting as a Lewis acid by accepting the electron pairs.
Nucleophiles and electrophiles

Organic compounds are predominantly covalent and many organic reactions result
from processes involving the breaking of covalent bonds and the making of new
ones. Reaction mechanisms, such as nucleophilic or electrophilic substitutions, also
involve electron pair transfers and can therefore be described by the Lewis acid–base
theory (see section 20.1.1 (/schoolstaff/app/chemistry-hl-2016/book/organic-
ahl/types-organic-reactions/nucleophilic-substitution-reactions/) & section 20.1.3
(/schoolstaff/app/chemistry-hl-2016/book/organic-ahl/types-organic-
reactions/electrophilic-addition-reactions/)). The reaction between water and a
carbocation shown in Figure 4 involves one of the electron pairs from the
oxygen being used to make a new sigma (σ) bond to the central carbon in the
carbocation.
Figure 4. Water acting as a nucleophile (and Lewis base) in a substitution reaction

(SN1).
This type of interaction is seen in the second stage of the SN1 mechanism of
nucleophilic substitution (section 20.1.1 (/schoolstaff/app/chemistry-hl-
2016/book/organic-ahl/types-organic-reactions/nucleophilic-substitution-reactions/)).
The water molecule is acting as a nucleophile in that it is attacking the electron-
deficient centre of the carbocation, but in the same instance, it is acting as a Lewis
base. Likewise, the carbocation is acting as an electrophile and a Lewis acid.
 International Mindedness
The development of acid–base theories
Arrhenius theory – 1880s
The Swedish scientist Arrhenius was the first to link acidic behaviour to
the presence of hydrogen and to the concept of ions in solution. He
proposed that acids were compounds that produced hydrogen ions in
solution and bases were substances that produced hydroxide ions in
solution. Neutralisation occurs when these two – hydrogen ions and
hydroxide ions – react to produce water. There were several reasons,
however, why this theory was viewed as not being totally satisfactory.
For instance, some compounds with acidic properties did not contain
hydrogen, while some bases were found not to contain hydroxide ions.
Also, the theory was only applicable to solutions in water.
Brønsted–Lowry theory – 1923
As a result of the shortcomings of the Arrhenius theory, chemists sought

other explanations for the nature of acids and bases. The Brønsted–
Lowry theory was put forward independently by the Danish chemist
Johannes Nicolaus Brønsted and the English chemist Thomas Martin
Lowry. This theory stated that any compound capable of transferring a
proton to another was an acid. Conversely, a compound capable of
accepting a proton was a base. This theory resolved some of the
problems with the Arrhenius theory and explained the behaviour of all
the acids and bases covered by that theory. For instance, Brønsted–
Lowry theory is not restricted to aqueous solutions. This idea of
conjugate acid–base pairs is an important part of the Brønsted–Lowry
approach.
Gilbert Lewis – 1923
An even more general definition of acids and bases was envisaged by the
approach of Gilbert Lewis. His theory was developed because of the
problem of substances which show acidic properties in solution (for
example, CO2) but do not contain an H+ ion. Lewis defined an acid as any
compound that could act as an electron pair acceptor and a base as any
compound that could act as an electron pair donor. In this Lewis scheme,
H+ itself is an acid.
Usanovich – 1939
Mikhail Usanovich proposed an even more general approach to acid–

base theory. He defined an acid as any chemical species capable of
combining with anions or electrons or releasing cations. Conversely, he
defined a base as the opposite of this – any chemical species capable of
releasing anions or electrons or combining with cations. This definition
encompasses all Lewis acids and bases and indeed all redox reactions.
For example, the synthesis or redox reaction:
2Na(s) + Cl2(g) → 2NaCl(s)
would be classed as an acid–base reaction under this Usanovich theory.

The base, a sodium atom, loses an electron; the acid, a chlorine
molecule, combines with this electron.
 Theory of Knowledge
Extension
This section invites the following Knowledge Questions:
How do explanations in Chemistry differ from those of other AOKs,

such as History?
Which other AOKs have multiple possibilities when explaining concepts
and phenomena?
Do we judge competing theories in terms of their universality,
simplicity, or elegance?
There are a number of different theories that are used to explain acid-
base behaviours, such as Brønsted–Lowry or Lewis, depending on which
perspective you take to explore the idea and the level of complexity that
you decide that you want to work to. We all know that theories and
explanations for the same phenomenon will become more complex with
elevated levels of study, but how do we know whether a particular
explanation is true or not? In Science, we first have to gather evidence
that then requires interpretation to form a hypothesis that then can be
tested. The hypothesis itself relies on our interpretation of the evidence
(which can involve a number of WOKs – which do you think scientists use
the most, and which do you?) So it could be argued that the findings are
subjective, at least to a degree. Furthermore, the same evidence could
have multiple explanations and hypotheses: so how do we judge which is
correct? Accurate? Valid? And how do these terms differ?
Watch the following video about alternatives to the big bang theory:
10 Alternatives To The Big Bang Theory
For each theory, what WOKs are they using to decide whether or not a
theory might be correct? How are the theories similar and/or different?
What conclusions can you draw about how we judge and, in turn, value
competing scientific theories?
  
Checkpoint questions
+ Show 4 questions
Checklist
 What you should know
At the end of this Subtopic 18.1 - Lewis acids and bases, you should be
able to:
recall the Brønsted–Lowry definitions of an acid and a base in

terms of the transfer of protons (H+ ions),
understand that the Lewis definition of an acid and base involves
the transfer and acceptance of an electron pair, and involves the
formation of a coordinate covalent bond,
understand that this definition of acid–base behaviour broadens
our understanding of such behaviour to include reactions that do
not necessarily involve proton transfer, and
understand that the range of Lewis acid–base reactions also
includes organic reactions involving nucleophiles (Lewis bases) and
electrophiles (Lewis acids) and that the 'curly arrow' annotation for
organic reaction mechanisms shows the type of transfer of
electron pairs envisaged by the Lewis definitions.
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5/22/2018 Book | Kognity

The big picture

A fundamental reaction type

Figure 1. The structure of the heme group in hemoglobin showing the coordinate

Once captured, the precious oxygen is transported in our bloodstream to be released

Figure 2. A visual model of the oxygen-binding process, showing the remarkable

Suffocation by carbon monoxide (CO) poisoning is another Lewis acidbase reaction.

Lewis theory of acids and

A Lewis acid is an electron pair acceptor.

The electron-deficient compound boron trifluoride, BF3, is a good example of a

Figure 1. The formation of the adduct between ammonia and boron triﬂuoride;

Theories can be supported, falsiﬁed or replaced by new theories – Lewis

Early deﬁnitions of acidity associated this property with the presence in

electronic arrangement and availability for bonding. The Lewis theory

A Brønsted–Lowry base is a particular example of a Lewis base that uses

One interesting example of Lewis acid–base behaviour is shown by the aluminium

Figure 2. The formation of the Al2Cl6 molecule.

Nucleophiles and electrophiles

Figure 4. Water acting as a nucleophile (and Lewis base) in a substitution reaction

The development of acid–base theories

Arrhenius theory – 1880s

Brønsted–Lowry theory – 1923

As a result of the shortcomings of the Arrhenius theory, chemists sought

Gilbert Lewis – 1923

Mikhail Usanovich proposed an even more general approach to acid–

2Na(s) + Cl2(g) → 2NaCl(s)

would be classed as an acid–base reaction under this Usanovich theory.

This section invites the following Knowledge Questions:

How do explanations in Chemistry diﬀer from those of other AOKs,

10 Alternatives To The Big Bang Theory

 What you should know

recall the Brønsted–Lowry deﬁnitions of an acid and a base in

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