1

Overview on Acido-Basicity

1.1 BACKGROUND: ACIDO-BASICITY THROUGH THE AGES [ 1-25]

Historically, acid substances have been known to man for more than 3,000 years, when vine-
gar was used for the first time in Mesopotamia. At more or less the same time, the Egyptians
used natron, a double basic salt of sodium carbonate and bicarbonate, for mummification and
in the manufacture of glass. In the Middle East, quicklime obtained by calcination of lime-
stone was first used to remove the grease and hair from leather, then in the manufacture of
cement. The term “acid” comes from the Latin acidus (sour) and the term “alkali” is derived
from the Arabic ul-guliy, plant ashes from which potassium carbonate (or potash) was
extracted by lixiviating. Unlike the term “acid”, which dates back to Antiquity, the term “base”
is much more recent: it appeared in 1736, used by Henri-Louis Duhamel du Monceau, a mem-
ber of the French Acadtmie des Sciences, who managed to isolate the fixed alkali contained
in sea salt and forming its base. Rouelle was later responsible for its more widespread use.
The era of alchemy, continuing well beyond the Middle Ages, made no significant contri-
bution to science as regards the understanding and rationalisation of chemical phenomena. In
this respect, the alchemists - especially the Western alchemists - who were primarily con-
cerned by the search for the philosopher’s stone, which would have the power to turn base met-
als into gold, and the elixir of life, remained particularly sterile until the 16‘h century. It is
worth pointing out, however, that alchemy did not concentrate solely on chemistry, making a
non negligible contribution to experimental “know-how” on the discovery and control of var-
ious instruments (alembic, aludel, cornue, retort, crucible, cucurbite) and techniques (luting
[to seal], decoction, crystallisation,purification, metallurgical techniques, etc.) used by scien-
tists at that time. This contribution is mainly due to Arab alchemists such as Jlbir ibn Hayyln
(or Geber) and Al-RAzi (or Rhazes), from the 8’ to the lothcentury. From the 10th century,
the Arab alchemists learned how to prepare and condense more and more powerful acids.
Before this time, only weak acids or solutions of corrosive salts were available. By treating
various salts (for example green vitriol or iron sulphate), they obtained acids known as “spir-
its” due to their volatility: nitric acid (spirit of nitre or aqua fortis), hydrochloric acid (spirit of
salt, or later muriatic acid), sulphuric acid (known as spirit of vitriol or, if very concentrated,
6 Chapter I Overview on Acido-Basicity

oil of vitriol due to its high viscosity). They even managed to produce aqua regia, which could
dissolve gold. They also knew how to prepare various caustic alkalis such as NaOH (soda) and
KOH (potash), obtained by treating the corresponding carbonates with slaked lime, Ca(OH),.
Arab alchemy dominated until the end of the 13‘h century (the end of the Crusades), at which
time Arabic was the sole language used in science. Gradually however, the Western alchemists
drew inspiration from their Arab masters, and several discoveries are attributed to them:
ammonia, the action of nitric acid on metal salts, the preparation of new salts, etc.
At the start of the 17thcentury, the alchemists had left a heavy legacy. The nomenclature
of compounds known was complex and chaotic: the word “alkali” for example, designated
both soda and potash, whilst potassium sulphate had two names: vitriolated potash and vit-
riolated tartar. The chemists themselves were going through a period of complete intellec-
tual confusion and anarchy. Although the 17thcentury was marked by the Renaissance and
the creation of Academies of Science (Florence in 1657, London in 1660, Paris in 1666,
Berlin in 1700), this situation was to remain for many decades. The 17* century therefore
witnessed a period of complex cohabitation between chemical doctrines, more or less vague
and contradictory. We find the alchemists who inherited traditions of magic and mystery
from their predecessors, the alchemists looking towards the future, for example Paracelsus
(1493-1541), the rationalistic chemists, those inspired by the Aristotelian doctrine’, the tech-
nician, artist and craftsman chemists, the doctors, the apothecaries and the metallurgists.
Many “scientists” built their science around their own theories, often peppered larger or
smaller doses of religious or mystical beliefs, astrology, magical practices or pseudo-scien-
tific inventions. Nevertheless, out of this chaotic and confused scientific world there
emerged several brilliant figures, such as Robert Boyle, Nicolas Ltmery and Van Helmont,
who were to make significant contributions to science.
The period starting with the 17th century saw the development of numerous theories on
acidity and alkalinity. Of these theories, the two most important are probably the corpuscle
theory and the theory of mixtures (a mixture is a chemical combination), or chemistry of
principles.
From 1620the Frenchmen Bitaud and de Villon then, a few years later, the German Sennert
and the Frenchman Basso revived old atomistic and corpuscular theories proposed back in
Antiquity by Greek philosophers (Plat0 and Democntus of Abdera, some 350 to 450 years
BC). They were followed by Gassendi in France and especially Robert Boyle in England who
put forward a general theory which interpreted all physical and chemical phenomena on the
basis of a change in size, shape, combination and movement of corpuscles of elementary mat-
ter (the corpuscular philosophy). Contemporaries of Boyle, especially Saint-Andre around
1680, Homberg and Ltmery around 1690, further refined this mechanistic concept: the acid
particles had small, very fine needles whereas the alkalis contained small pores, neutralisation
took place when the spikes of the acids were inserted in them. The strength of an acid
depended on how fine the spikes of its particles were. Nicolas Ltmery (1690), an excellent
speaker and teacher, portrayed this mechanistic description of acidity and alkalinity in the 7th
edition of his Course of Chymistry, a book which experienced overwhelming popularity at the

1. The four fundamental elements associated with the four fundamental qualities are: water (cold and moist), earth
(cold and dry), air (hot and moist) and fire (hot and dry).
 Chapter 1 Overview on Acido-Basicity 7

time. Various different points of view were held however. Lkmery believed that acidity was
lost in a reaction since it is brittle and therefore destructible. In Homberg’s opinion, on the con-
trary, acidity is not destroyed by neutralisation but simply hidden and it can be regenerated
the acid spikes can come out of the “alkaline sheath”. The mechanistic view of acidity and
alkalinity endured for a considerable time, almost until the end of the 1gth century (fig. 1.1).

I ACID
Chemists define the Acids as stifL long, pointed, sharp bodies
able to enter types of porous and spongy sheaths or bodies
which they call “alkalis”. To gwe a n illustration of acids and
alkalis, they used to compare a n Acid inside a n alkali to a
sword put into its scabbard. On this occasion, they point out
very wisely that such bodies are Acids with respect to Alkalis,
and Alkalis with respect to Acids. 7he Acids are found in the
h r t h , Plants and Animals. The first are k n m as “Mineral
Acids”, the second as “Vegetable Acids” and the third as
“Animal Aclds”. Vitriol, Nitre, etc. contain many mineral
Acids; most Plants and especially Aromatic and Marine
Plants, many fruits, such as lemon, gooseberry, etc. yield
numerous vegetable Acids; lastly, animal bodies, whatever the
species, necessarily contain a hrge number of acids, most of
which are used in digestion. The article on fermentations
indicates the roles played by Acids and Alkalis in nature and
the physical reason pushing one inside the 0 t h .

Fig. 1.1 [I71

Dictionaly of Physics dedicated to the king, reviewed, corrected and enriched
with discoveries made in this science since the year 1773 (edition reviewed by
Mr. Aimt-Henri Paulian, priest at the Nimes Royal Academy and the Lyon
Royal Agricultural Society in 1781).

The opposition between acids and alkalis had been known as far back as 1620: Van
Helmont had accepted that the union of an acid with an alkali could result in a salt, thereby
taking a lead of almost a century over Rouelle’s definition of salts. In 1664, Boyle estab-
lished a new classification of compounds, with three classes: acids, alkalis and salts. Stating
that the elements should no longer be considered as properties but as primitive and simple
bodies, he introduced the notion of principle elements, from which the mixtures (or “mix-
ture” bodies) are formed. He also proposed a method to distinguish between acids and bases,
by observing the colour change to a solution of violet syrup when the acid or base is added.
At more or less the same time, Glauber managed to differentiate between soda and potash
and identified muriatic acid.
8 Chapter I Overview on Acido-Basicify

Towards the end of the 1 7‘h century, the chemist physician Georg Ernst Stahl set forth an
antimechanistic chemical doctrine based on traditional terms such as “mixture” (chemical
reaction), “principle elements” (constituents of mixtures responsible for their characteris-
tics) and “affinity”. Stahl recognised two principles for all mixtures: water and earth, whilst
distinguishing between the three types of earth proposed by Becher shortly before (vitrifi-
able earth, combustible earth and mercurial earth). If the acids have an affinity for the met-
als and attack them, this is due to the fact that they share a principle with them. Certain
scientists held the view that only one universal acid principle existed - Stahl was convinced
that it was sulphuric acid - there being an excess of this principle in the acids and insuffi-
cient in the alkalis. Neutralisation resulted in redistribution of this principle between the two
substances. Others, on the contrary, were convinced that there were two universal principles,
one acid, the other alkaline, neutralisation resulting from their mutual destruction.
The 1 century is marked firstly by the theory of phlogiston proposed by Stahl in 1702,
resulting directly from his chemistry of principles, and secondly by Lavoisier’s opposition to
this theory. Phlogiston, or inflammable principle, an imprecise concept devised to explain
the phenomena of corrosion of metals and combustion, is an extremely subtle material
involved in the composition of all bodies in different proportions, conferring on them their
colour and odour, and which, being released by combustion, explains the change in appear-
ance and energy given off. Sulphur, considered as being a combination of sulphuric acid and
phlogiston, released phlogiston during combustion thereby producing the acid (Trait6 du
soufre, by G.E. Stahl, in 1716). The same phenomenon occurred with phosphorus. Aristote
had used the term phlogiston for the first time in Antiquity to designate combustion accom-
panied by flames. Stahl borrowed this term to describe the capacity of combustible earth (or
Becher’s terra penguis) to bum and its behaviour during combustion. Generally, the bodies
which, like some reducing agents (charcoal, sulphur), burnt leaving very little residue were
species rich in phlogiston; conversely, those which, like the metals and the alkalis, left a
large amount of residue were species with very little phlogiston. Neutralisation of an acid by
a base consisted of a redistribution of phlogiston between the two species. To explain and
establish that its disappearance corresponded to an increase in weight, some advocates of
phlogiston said that it was lighter than air (principle of lightness), whilst others suggested
that it had a negative weight. In the theory of phlogiston, combustion is therefore presented
as a subtraction. In some respects, this theory is the reverse of the oxidation-reduction the-
ory which appeared later.
At the end of the lgthcentury, Lavoisier explained the phenomenon of combustion firstly
in terms of an increase in weight due to the combination with oxygen (oxygen was discov-
ered almost at the same time by Scheele and Priestley in the 1770’s) and, secondly, in terms
of the release of energy, quantifiable by accurate measurements. He strongly denounced and
disproved the theory of phlogiston, first in his famous paper Rkjlexions sur le phlogistique
published in 1785, then in the Traitd dlkmentaire de chimie which appeared in 1789. He also
has the merit of being the first person to attempt to give a scientific explanation of acidity.
Having observed that most compounds obtained by combustion were acidic, he deduced that
the acidity of these compounds is related to the presence of oxygen. However, he placed too
much emphasis on the role played by oxygen and as a result, imposed the idea that this ele-
ment must be present in a compound if it is to be acidic: an acid compound necessarily had
 Chapter 1 Overview on Acido-Basicity 9

to be oxygen-rich. The word “oxygen” was in fact created by Lavoisier to express its most
remarkable property: oxygen is the substance which generates the acids. The word was offi-
cially introduced into the chemical vocabulary in 1787 with the redefinition of chemical
nomenclature imposed by Lavoisier, with the support of several famous scientists he man-
aged to convince: Guyton de Morveau, who had just completed his Encyclopidie de la
chimie, and two former phlogiston proponents, Berthollet and Fourcroy. This new theory,
known as the “theory of oxygen”, based on the oxygen-acidity duality, was also supported
by the Swedish chemist Berzelius and prevailed until the end of the lSth century.
The second half of the lSthcentury was marked by the start of the first Industrial revolu-
tion (known as the paleotechnical revolution), associated with the use of coal and the inven-
tion of the steam engine. It corresponds to the emergence of large-scale industry, especially
that of chemistry. The first sulphuric acid works (vitriol works) were first built in England,
before 1750, then in France, at Rouen, where the industrialist Holker installed the first lead
chamber in 1766. By 1782, France had three vitriol works. The development of the soap and
glass industries created a large demand for alkalis. The first soda works (at the time, soda
was still a synonym for sodium carbonate), built at Saint-Denis in 1792 by Nicolas Leblanc,
marked the effective beginning of the large-scale chemical industry. Leblanc’s invention
concerning “the manufacture of soda extracted in large quantities from sea salt”, described
in a patent application registered on 19 September 1791, was the first to benefit from the
new law of 7 January 1791 on the inventor’s right of ownership for fifteen years [ 191. At this
time, the rule was that the content of the patent should remain secret during this fifteen year
period, but following a decision made by the Public Welfare Committee, the content was dis-
closed and placed at the disposal of the nation in 1793, thereby ruining Leblanc [19]. The
Leblanc process, however, was to remain in use until the start of the 20th century (the last
Leblanc soda works was shut down in 1914), in spite of several major disadvantages: coal
consumption was high, the quality of the sodium carbonate manufactured was mediocre and
calcium sulphide, a worthless by-product, is produced.
Lavoisier is often considered as the founder of modern chemistry. Yet, at the time of his
execution on 8 May 1794 during the Terror, there remained many opponents to this new
chemistry. It took another twenty years before the new chemistry was established in Europe,
due in particular to the reopening of the Academy and the endeavours of its disciples, includ-
ing Chaptal and Fourcroy. The traditionally imprecise and confused language of the old
chemists progressively disappeared to be replaced by a clearer and more precise language,
based on Lavoisier’sMkthode de la nomenclature.
At the start of the 19thcentury, Lavoisier’s theory of oxygen slowly evolved, especially
due to Berzelius, into a more general theory known as the “generalised dualistic theory”,
“electrochemical dualism”, or “electrochemical theory of combination” whereby oxygen, in
particular, could be replaced by all electronegative bodies as constituents responsible for
acidity. According to the electrochemical theory of combination, a very broad theory extend-
ing well outside the scope of acido-basicity, every body, whether simple or compound, was
characterised by a positive or negative electrical polarity whose intensity varied depending
on the type of body. The degree of affinity of the simple bodies was determined by the charge
they camed and the chemical reaction was defined as the simple union of two opposite
forces. The combination of two bodies was seen under this theory as a chemical addition.
10 -
Chapter 1 Overview on Acido-Basicity

By replacing in the 18 lo’s the theory of oxygen by this broader theory, Berzelius saved it
from severe criticism. By the end of the 1 gthcentury and the start of the 1Sth, other scien-
tists had in fact moved away from Lavoisier’s theory. Berthollet in 1789 with prussic acid
(HCN), Davy in 1810 with muriatic acid (HCI), Gay-Lussac in 1815 and Dulong in 1816
with various acids, had observed that some of these acids contained no oxygen but that all
contained hydrogen. In the 18 1O’s, the idea that acidity was due to hydrogen and not to oxy-
gen gradually gained ground in the scientific community. By 1830, a few years later, eleven
hydracids not containing oxygen had already been identified, including the halogen acids
(HF had been discovered by Scheele in the second half of the Isthcentury), HCN, HSCN,
H,S, etc. Nonetheless, in spite of a few sporadic quarrels, there was practically no con-
frontation between the theory of hydrogen and the theory of oxygen, thanks to Berzelius’s
new electrochemical theory of combination and also, to a large extent, its author’s strong
personality. It was also during this period, in 1835, that Berzelius invented the word “catal-
ysis” to qualify the change in rate of chemical reactions which occurs in the presence of cer-
tain substances [ 1,241. He published several articles stating his views on the effect, not yet
understood, of a change in the rate of chemical reactions, which could not be explained by
the theory of chemical affinity and which seemed to be due to the mere presence of various
substances [25], including acids such as sulphuric acid (catalyst in the hydrolysis of starch
or the dehydration of alcohol for example). As part of his dualistic theory, he claimed in
1843 that this mysterious force (catalysis) was due to the electrochemical properties of these
substances. Other interpretations were also to be proposed, but it was only much later, at the
start of the 20thcentury, that the first satisfactory theories on catalytic effect were formu-
lated. When this effect was identified, the lead chamber process for the synthesis of sul-
phuric acid from sulphur and saltpetre had already been in use for almost a century, yet no
scientist had noticed the action of catalytic promotion. From the 1870’s, the lead chamber
process was progressively replaced by the catalytic oxidation of sulphur dioxide on platinum
catalyst. In 1838, Kuhlmann made an observation which was to mark the true origin of the
catalytic process for the synthesis of nitric acid by oxidation of ammonia, even though the
first unit implementing this process only started after 1910 [ I , 241.
Around 1840, the generalised dualistic theory also began to reveal its limitations, and even
though Berzelius was still held in considerable esteem at the time, it was to face increasing
competition from a new theory: that of substitution.In 1836, Berzelius’s electrochemical dual-
ism, which had so far been accepted as a dogma, was suddenly disputed by a young scientist,
Auguste Laurent, who demonstrated that the electropositive element hydrogen in a hydrocdr-
bon could be replaced by an electronegative element chlorine (synthesis of trichloroacetic
acid), which was totally impossible with Berzelius’s theory. His teacher, Jean-Baptiste Dumas,
had already made this observation and had stated an “empirical law of substitution” as early
as 1834, without seeking a confrontation with Berzelius. Being young, Laurent found no sup-
port and finally the recognised masters of chemistry, Liebig and Dumas, helped by the death
of Berzelius in 1848, quietly put an end to “electrochemical dualism”. Liebig, drawing inspi-
ration from Davy and Dulong, proposed in 1837 that the acids are certain hydrogenated com-
binations in which the hydrogen can be replaced by metals. A little later, Gerhardt wrote than
an acid was a hydrogenated body in which the hydrogen could easily be exchanged by double
decomposition against an equivalent quantity of metal, thereby postulating that a salt is
formed by a substitution reaction and not by addition, as was advocated by Berzelius’s theory.
 Chapter I - Overview on Acido-Basicity 11

Developing a new symbolism and establishing chemical formulae for the known com-
pounds which would be as accurate and as clear as possible, to represent the conversions of
matter qualitatively and quantitatively, was one of the paramount concerns of chemists in the
1gthcentury, especially during the second half. This period also witnessed another important
step in the understanding of chemical phenomena: the distinction between atoms and mole-
cules. Concerning this point, the contribution made by scientists such as Cannizzaro first
then Meyer, with his work on the modern theory of chemistry in 1864, was decisive.
Mendeleyev's first periodic table of the elements, presented in March 1869 to the Russian
chemical society, is no less an achievement. Initially, this version and the later improved ver-
sions found virtually no success, but the discovery of gallium by Lecoq de Boisbaudran, in
1875, finally gave the periodic table the recognition it deserved.
The other key event marking this period is the second Industrial revolution, which took
place towards the start of the second half of the 19'h century and which is generally associ-
ated with the discoveries of electricity and oil and with the success of chemistry.After a cen-
tury of noticeable development, industry experienced rapid growth, especially the chemical
industry (glassware, colouring agents, artificial textiles, celluloid, drugs) where hydrochlo-
ric, nitric and sulphuric acids and bases such as ammonia and caustic soda NaOH played an
important role. This growth was one of the main factors involved in the industrial expansion
at the start of the 20th century. One of the most remarkable achievements was the replace-
ment of the Leblanc sodium carbonate manufacturing process by the Solvay process [ 191. In
1861 Ernest Solvay, a 23 year old employee in his uncle's gas works near Brussels, devel-
oped his process using ammonia and patented it. After numerous setbacks, in 1869 he
demonstrated its superiority over the Leblanc process, building his first soda works in 1874
at Dombasle-sur-Meurthe,in Lorraine, a region rich in the two main raw materials: salt and
limestone (coke was transported by barge on the Marne-Rhine canal) [19]. Still today,
sodium carbonate is a product required in many applications: glassware, enamelware, pho-
tography, iron and steel, chemical industries, textiles, detergents, dyes, tanning, food (sweet-
ening and sugar juices), pharmacy, agriculture, etc.
The manufacture of ammonia-based fertilisers started in the 19'h century, speeding up
towards the end of the century with the emergence of industrial methods to manufacture this
base (processes using cyanamide and nitric oxide). It was in the early 20thcentury, however, in
1913, that a new revolutionary method was developed: the direct synthesis of ammonia by
Haber and Bosch using nitrogen from the air and hydrogen from water gas, on an iron catalyst.
Electrolysis, which appeared at the end of the century, was used to prepare soda NaOH
and chlorine from sodium chloride. The end of the 19'h century was also marked by the
important discovery made by Charles Friedel and James Mason Crafts who observed, in
1877, the auto-accelerated formation of aluminium chloride and amylbenzene in a mixture
of amyl chloride and benzene in contact with aluminium filings: they had just demonstrated
the catalytic role played by aluminium chloride, which was to be identified in the 20thcen-
tury as a strong Lewis acid.
In spite of the considerable progress made in the field of chemistry, both in terms of sci-
entific knowledge and the development of industrial applications, the reasons for the acido-
basic properties of substances, many of which known for hundreds and even thousands of
years, were still obscure long after the middle of the 19' century.
12 Chapter I Overview on Acido-Basicily

The first true modem theory of acidity appeared in 1887. Published in the thesis of the
young Swedish chemist Arrhenius, which at first received little support, this theory was
based on electrolytic dissociation in aqueous solution and claimed that acidity was due to
the proton H'. Whilst nearly five thousand years had elapsed between the time when man
had become aware of the existence of acids and the time when hydrogen was identified as
being the source of acidity, it took much less than a century to realise that acidity is in fact
due to the proton from the hydrogen. After Arrhenius's thesis, it took less than forty years to
demonstrate that the proton is far from being the sole source of acidity. At the start of the
20thcentury, other theories were to emerge, with two main objectives in mind with respect
to Arrhenius's theory:
- make it more general (to include a wider range of known reactions);
- improve its quantitative nature (in order to predict as accurately as possible the reac-
tivity between compounds).
In simple terms, we can say that there are currently three major categories of modern the-
ories on acido-basicity, based respectively on:
- electrolytic dissociation of molecules in a solvent (the Arrhenius and Bramsted-Lowry
theories);
- the electronic theory (Lewis acido-basicity theory);
- the electronic theory and quantum mechanics: modem approach of Pearson's HSAB
(Hard and SoftAcids and Bases) principle, for example.
Brief descriptions of these modem theories of acidity are given in section 1.2 below.

1.2 ACIDO-BASICITY THEORIES

1.2.1 Arrhenius's Theory (1887). Acido-Basicity of Aqueous Solutions

According to Arrhenius, acids are compounds which when dissolved in water give rise to the
formation of hydrogen ions, as for example with hydrochloric acid:
HCI -+ H+ + CI
and bases are compounds which give rise to the formation of hydroxyl ions OH-, as for
example with sodium hydroxide:
NaOH -+ Na' + OK
The neutralisation of an acid and a base forms a salt and water (which is also the solvent):
HCl + NaOH + NaCl + H,O
Using Arrhenius's definition, in 1909 the Danish chemist Sorensen drew up a scale of
acidity based on the value of the logarithm of the concentration of free hydrated H+ ions in
water:
pH =-log [H']
 Chapter 1 Overview on Acido-Basicity 13

Although it provided a means of comparing acids and bases in aqueous solution, this the-
ory already presented various disadvantages which led to investigation into more general
theories:
- The acids were limited to compounds containing hydrogen. Compounds such as SO,,
CO,, etc. were excluded.
- Acid-base behaviour was not recognised in non-aqueous solvent. This theory implied,
in fact, electrolytic dissociation of the compounds considered in water, hence an obvi-
ous shortfall with non-ionising solvents (e.g. HCI in benzene). For the same reason,
anhydrous HCI was not considered as an acid.
- NH, was not considered as a base in the absence of water. In the presence of water,
formation of the basic molecule NH,OH was necessary, since only this could dis-
sociate to form the OH- ion.
- Lastly, Arrhenius's theory assumed that the proton is free in the solvent water, whereas,
already at the end of the 19" century, it was known that there was an association
between protons and the molecules of various solvents (e.g. water and ethanol).

1.2.2 Brsnsted-Lowry Theory (1923). Ideal (Dilute) Solutions [4,26-30]

1.2.2.1 Definitions
In 1923, Brsnsted and Lowry independently reached a more generalised model of the acido-
basic reaction. This model, which results from the fact that the proton cannot exist free in a
solvent, differs from Arrhenius's theory on several points:
The acid-base reaction is defined as being a proton transfer from the acid to the base (pro-
tolysis). An acid is a compound which can donate a proton to a base and a base is a com-
pound which can accept the proton from an acid. Molecules such as NH, and the acetate ion
CH300-, which are not bases according to Arrhenius, become bases according to the
Brsnsted-Lowry theory. Moreover, in the Brsnsted-Lowry theory, the true base in aqueous
solutions of NaOH or KOH is not the alkaline hydroxide but the OH- ion.
Some examples of acids according to the Brsnsted-Lowry theory: H,O+, NH;, HCI,
CH3COOH, H,O, HCOj, HSO,, C H OH, etc.
'2-
Some examples of bases: SO$-, C03 ,OH-, CH,COO-, C6H,0-, CI-, NH,, H,O, CH,OH,
C,H,OC,H,, etc.
The acid is no longer considered in isolation but as one of the two partners necessary to
perform the acid-base reaction. Its behaviour depends on the basic partner present with it.
The dissociation of an acid in a solvent is considered as an acid-base reaction: the proton
released by the acid attaches to a solvent molecule to form a lyonium ion.
The notion of solvent is extended: numerous molecules other than water may behave as
solvents. In this respect, several groups of solvents can be identified [28]:
- The protic solvents, which are both protogenic (proton donor) and protophilic (proton
acceptor). Water, the alcohols, carboxylic acids, liquid ammonia, the primary and sec-
ondary amines, etc. behave in this way. They are also known as amphiprotic solvents.
14 Chapter 1 Overview on Acido-Basicity

- The solvents which are protophilic but not protogenic such as the ketones, ethers, di-
N-substituted amides, some esters, etc. Dissolution of an acid in these solvents is an
acid-base reaction within the Brernsted-Lowry meaning since the protophilic solvent
can accept the proton from the acid. Conversely however, dissolution of a base in these
solvents is not an acid-base reaction within the Brernsted-Lowry meaning since the
non-protogenic solvent does not have a proton to donate to the base. Some solvents,
which strictly speaking are protogenic due to one of the hydrogen atoms of the mole-
cule, cannot however be considered as normal amphiprotic solvents since this proto-
genic nature is so weak that degradation generally accompanies the elimination of this
atom. Such solvents are therefore classified in this second group.
- The aprotic solvents which are neither protogenic nor protophilic, such as phosphorus
oxychloride and liquid sulphur dioxide. In this group, certain solvents such as ben-
zene, chlorobenzene, chloroform, etc. are practically inert. Solvents which could be
included in the previous groups, but whose protophilic and protogenic characteristics
are so low as to be virtually non-existent, are also included in this category.

1.2.2.2 Special Property of the Proton [3 I ]

The proton is the only univalent cation whose dimensions are the same as that of the atomic
nucleus, which is roughly a hundred thousand times smaller than the other ions. When a
molecule approaches, the repulsion which generally occurs between the electron clouds does
not exist with the proton. Moreover, the proton exerts a strong electric field in its neigh-
bourhood and consequently an extremely powerful polarising action. This unique character-
istic makes it extremely reactive, which explains why it cannot exist free amongst other
molecules. In both liquid and gaseous media, we can consider the protons as only being
present when associated with one or more categories of molecules present in the medium.

1.2.2.3 Conjugate Acid-Base Pairs

In view of the above, the acid-base reaction (or protolysis) is an equilibrium reaction in
which the equilibrium represents the way the proton is shared between two basic entities. In
its general form, the reaction between an acid HA and a basic molecule B is written:
H+A- + 6 w A- + BH+ (1.1)
In equilibrium, the proton is present in the two forms HA and BH'. The entity A- released
by loss of the proton is the conjugate base of the acid HA and the entity BH' formed by
accepting the proton is the conjugate acid of the base 6. The notion of conjugate acid-base
pair is one of the main concepts of the Brernsted-Lowry theory. The anions CI-, Br-and NO,
are therefore the conjugate bases of the acids HCI, HBr and HNO, respectively. Similarly,
H30f and NH; are the conjugate acids respectively of the bases H,O and NH3.
In a medium where the proton is shared between several basic entities, we can see intu-
itively that it will preferably be associated with the strongest base. An acid HA behaves as a
strong acid with respect to the base B if, at equilibrium, virtually all the molecules of this
base have accepted a proton to form the conjugate acid BH' (reaction 1.1 completely, or
nearly, shifted to the right). The conjugate base A- of the strong acid HA is, in this case,
 Chapter I Overview on Acido-Basicity 15

much weaker than the base B and the conjugated acid BH' of the base B is much weaker
than the acid HA.
Generally, a weak conjugated base corresponds to a strong acid (completely dissociated),
and inversely a strong conjugate base corresponds to a weak acid (slightly dissociated). In
water, C1- is the weak conjugate base of the strong acid HCl; H,O+ is the strong conjugate
acid of the weak base H 2 0 ; H 2 0 is also the weak conjugate acid of the strong base OH-.

1.2.2.4 Autoprotolysis
Some compounds, for example H20, HCO;, HSO,, NH,, etc., are amphiprotic or ampho-
teric, i.e. capable of behaving as either acids or bases depending on the partner presented.
Due to their amphiprotic nature, these molecules result in an autoprotolysis acid-base equi-
librium which can be written in the general case as:
HA + HA ($ H,A+ + A-
This equilibrium is characterised by the autoprotolysis constant Kapwhich, for water, is
equal to:
Kap= [H,O+] [OH-] = mo12/12at 25°C
Table 1.1 shows the logarithms of the autoprotolysis constants for various solvents at
25°C (pKap= -log Kap).

Table 1.1 Autoprotolysis constants of various solvents at 25°C.

Solvent H,SO, HCOOH CH,C02H HF H20 CH,OH C,H,OH NH,

pK,, 3.47 6 12.6 13.7 14 16.6 18.9 29.8

1.2.2.5 Acidities (Basicities) or Acid (Basic) Forces of an Acid (of a Base)

The general acid-base reaction 1.1 in a medium M can be described as two partial reactions
each involving a conjugate acid-base pair and each causing a proton of the medium to appear
(remember that the protons of the medium do not exist free isolated in liquid phase and that
they are therefore necessarily lost from a molecule of this medium) which we will write H&
to simplify:
H'A- + medium M u A- + H L (1 3
B+H+, e BH' + medium M (1.3)

H'A- +B w A-+BH' (1.1)

The dissociation constant (or protolysis constant) of the overall reaction 1.1 is written:

K = [A - I [BH+ 1
[HA1 P I
16 Chapter 1 Overview on Acido-Basicity

The dissociation constant KHA of the partial reaction 1.2, which includes the concentra-
tion (or strictly activity) term of the medium M (constant term if the acid and base concen-
trations are low: see below the case where the medium M is water, with the relation 1.7),
represents to a certain extent the strength of the acid HA in the medium M, i.e. its tendency
to donate its proton to the medium M in which it is placed:

where the term aHrepresents the protonic activity of the medium, i.e. the tendency of the
medium M to donate a proton to the conjugate base A- (see paragraph 1.2.2.6).
Similarly, the basicity constant KS of the base B in the reaction I .3 represents the basic
strength of the base in the medium M, i.e. its affinity for the protons of the medium:

The values of constants KHA and KB determined experimentally in the medium M are rel-
ative to this medium which, in this respect, can be considered as a reference. They would be
different in another medium (different solvent) and obviously cannot be determined in the
absolute, i.e. without a reference.
The relative acid strength of the acid HA of acid strength KHA (in the medium M) with
respect to the base B of basic strength K, (in the medium M) is expressed by the protolysis
constant of the overall reaction 1.1

The relative acidity constant (or relative acid strength) of the acid HA with respect to the
base B measures the degree of transfer of the proton from the acid HA to the base B and
depends on the tendencies of both partners to respectively donate and accept the proton. For
a given acid HA, the greater the acid strength of this acid and the greater the basic strength
of the partner base 6, the greater the value of K.
Water is generally chosen as reference to express the strengths of the acids HA or the
bases 6. The relative strength of the acid HA in water, i.e. its tendency to donate a proton to
the water, is then written:

Since the concentration of undissociated water molecules can be considered as constant

(55.5 molA at 25°C ) in diluted medium, the relative strength of the acid becomes:
 Chapter 1 Overview on Acido-Basicity 17

It is practical to express the relative strength of an acid by:

PK, = -log K, (1.8)
Considering the expression of pH in the Brransted-Lowry theory:
pH = -log [H30']
the expression 1.7 can be used to deduce the relation between pH and pK,:

(1.9)

For a base B dissolved in water, the acid-base reaction between the base and the water can
be written in general as:
B + H 2 0 w BH' + OH- (1.10)
hence the basicity constant (or basic strength) of B with respect to water:

In the special case where the base considered is the conjugate base A- of the acid AH,
relation 1.10 becomes:
A- + H,O w HA + OH-
The relative strength Kb of this base A- in water is written:

hence: K;Kb = Kap= [H,Of] [OH-] =

where Kq is the autoprotolysis constant of water in mo12/12(see paragraph 1.2.2.4).
Generally, the product of the strength K, of the acid AH in a solvent and the strength Kb of
the conjugate base A- of AH, in this solvent is equal to the autoprotolysisconstant of the solvent.
In order to classifL all the acid and basic compounds on a unique scale taking water as
the reference, we compare the bases by the acid strength of their conjugate acids BH':

(1.11)

1.2.2.6 Protonic Activity

In 1909, Sorensen defined pH for aqueous solutions as the cologarithm of the hydrated pro-
ton concentration. In the Brransted-Lowry formalism, it is expressed by:
pH = -log [H30']
18 Chapter 1 Overview on Acido-Basicity

where the Arrhenius hydrated proton H' is written in the form of the protonated solvent
H,O'. In practice, the experimental measurement of pH is based on the electromotive force
of a battery including a reference electrode and a hydrogen electrode. In this type of meas-
urement, however, it is the activity uH of the proton which is concerned, not its concentra-
tion, so accordingly in 1924 Sorensen's definition of pH was modified:
pH = -log [UH]

The activity uH of the proton has already been mentioned briefly in the previous section. In
a complex medium, with one or more solvents and several acid and/or basic molecules, the
protonic activity aH is not an activity in the usual thermodynamic meaning, related to a single
concentration by a single activity coefficient. It is a more complex quantity which must repre-
sent the part played in the overall acidity of the medium by all protons from the various more
or less acidic molecules of this medium. The mathematical expression of uH [3] can be deduced
from the previous relations 1.4 and 1.5 in the simple case of a &luted solution of an acid HA
or of a base B in a solvent S. The activities of HA and of B, and those of the entities resulting
from their dissociation or protonation, can therefore be compared with concentrations. If the
solvent S is the only basic molecule present opposite the acid, its activity is written:
fS.[SI
wherefs is the activity coefficient of the solvent whose concentration [S] is high, but can be
considered as constant to a first approximation. In this simple case, uH is written:

(1.12)

The electroneutrality of the medium implies that [A-] = [SH']. If the initial concentration
of the acid is C, the following equality is satisfied:
C = [HA] + [A-] = [HA] + [SH']
hence:

The only solution of this second-degree equation which has a physical meaning is:

(1.13)

uH, which represents the acidity of the medium, depends both on the strength of the acid HA
(by the acidity constant KHd and the strength of the protonated solvent SH' (conjugate acid
of the basic solvent). The protonic activity uH is therefore clearly due to all the linked protons
 Chapter 1 Overview on Acido-Basicity 19

of the medium, irrespective of the bases to which they are linked (A-or S). It is caused by the
activity of the small proportion of protons linked to the weakest bases, as well as the large
proportion of protons linked to the strongest bases. It is the resultant of two separate terms:
- a term of acid strength including the values of acid strength KHA and KSH+,expressing
the overall tendency of the mixture of entities HA and SH+to release its protons;
- an overall concentration term C: we can see intuitively that the higher the initial con-
centration C of the acid HA,the greater the protonic activity of the medium.
In relation 1.13, two extreme cases can be identified:
- slightly basic solvent S whose conjugate acid is stronger than the weak acid HA
(KSH+ KHA):

hence:

The higher the acid strength of HA and the lower the basic strength of the solvent S,
the greater the value of u,;
- strongly basic solvent whose conjugate acid is much weaker than the acid HA
(KsH+4 KHA):

hence:

i.e. UH C.KsH+ (1.14)

In this case, uH only depends on the acid strength of the entity SH', the weak conju-
gate acid of the strong base S.
As shown by relation 1.6 (K = KHA. KB),the protolysis constant (or the degree of transfer
of the proton of HA to S, or also the relative acid strength of HA with respect to S) is inde-
pendent of the protonic activity uHof the medium. In the same way as the acid strengths KHA
and Ks cannot be determined experimentally in the absolute but only in a chosen medium
acting as reference (see paragraph 1.2.2.8), a reference must also be chosen in order to meas-
ure the activity u,.

1.2.2.7 Levelling Effect of a Solvent

Relation 1.14 shows that the protonic activity of a medium composed of a strong acid in a
sufficiently basic solvent S only depends on the weak conjugate acid SH+of the solvent S.
The solvent levels the acidity: all the protons are in fact attached to the solvent molecules
and only the acid lyonium ion S H', whose acidity strength is lower than that of HA,is pres-
ent. The lyonium ion SH' is therefore the strongest acid remaining in the medium.
Consequently, in an aqueous solution of hydrochloric acid completely dissociated into
H,O+ and C1- ions, the strongest acid present in the medium is the hydronium ion H,O+.
Similarly, a base with high basic strength with respect to that of water will be completely
protonated by the water (reaction l.lO), creating an equivalent number of hydroxyl ions
OH-:the strongest base present in the medium is then OH-. This situation will be observed
20 Chapter I Overview on Acido-Basicity

with all the strong acids, which therefore cannot be discriminated in water solvent; the same
applies for the strong bases.
The acids (and bases) of different strength can therefore only be discriminated within a
limited range of strengths expressed in pK, (relation 1.8). The extent of this range obviously
depends on the acido-basicity characteristics of the solvent.
How can we determine the limits of this range of pK,? We have seen that H30+and OH-
are respectively the strongest acid and the strongest base which can be present in water. The
limits of the range of pK, are therefore set by the pK, of the acid H30f and the pKg of the
conjugate acid of the base OH-, i.e. the acid H20. To determine these limits, we must con-
sider the conjugate acid-base pairs H30+/H20(which is equivalent to the pair H+A-/A- in
reaction 1.2) in acid medium and H20/OH- (which is equivalent to the pair BHf/B in reac-
tion 1.3) in basic medium. As with reaction 1.2, the acido-basic reaction corresponding to the
pair H+A-/A- is therefore written:
H30f + H 2 0 e H 2 0 + H30+
where H30f is an acid and H 2 0 a solvent.
The constant K, in the pair H30f/Hz0is written by including the concentration of the sol-
vent H 2 0 in the equilibrium constant:

hence the pK, of the acid H30t:

PK, = -log 55.5 = -1.74
Similarly, the acido-basic reaction corresponding to the pair BH+/B (i.e. to the pair
H20/OH-) is written:
H 2 0 + HzO e OH- + H30f
where the first term H 2 0 is the conjugate acid of the base B = OH- and the second term H 2 0
the solvent.
Hence the constant Paof the acid HzO (conjugate of the base OH-) in the water solvent:
K g = [OH-] [H30']/[H20] = 10-14/55.5= 1.8.10-16
Hence: pKg= 14 + 1.74 = 15.74
The range, or scale, of pK, containing the measurable pK, values of the acids or bases in
the water solvent is therefore strictly: -1.74 > pKa > 15.74. As a first approximation, how-
ever, we generally estimate that in practice the usable range lies between 0 and 14.
We will now consider the base OH-. Its basic strength KL is expressed from the acido-
basic reaction corresponding to the pair OH-/H20:
OH- + H2O @ H2O + OH-
hence: KL= [H20] [OH-]/[OH-] = [H20] = 55.5

Consequently, the pKL of the base OH- is equal to:

pKL= -1.74
 Chapter 1 Overview on Acido-Basicity 21

In view of what was said in paragraph 1.2.2.5, we can see that:

pKa+ pKi= 15.74 - 1.74 = 14

1.2.2.8 Relative Classification of Acids and Bases:

Universal Acido-Basicity Scale Based on pK,
Acids and bases can be compared in terms of relative acid strength by using their pKa val-
ues in a given medium, generally water. The previous relations 1.7 and 1 . 1 1 show that, for
an acid HA, pKa represents the relative acidity strength of this acid directly whereas for a
base B, pKa represents the relative acidity strength of the conjugate acid BH' (as in the pre-
vious example where H,O is the conjugate acid of the base OH-) of this base (pKa = pKeH+).
If we want to use as the unique scale of relative acidity that obtained in the water solvent,
for example, discrimination of acids and bases is only possible in practice in the range of
pK, values between 0 and 14. To discriminate acids of pKa < 0 and bases of pKa > 14, other
solvents must be used to complete the scale. However, there is no reason why the pKa of an
acid (or a base) measured in water should be the same as the pKa of the same acid measured
in another solvent. Generally, the two pKa values will be separated by a ApK,, which must
be taken into account to position the acids (or bases) correctly on the unique scale. At this
stage, we are faced with a complication due to the type of solvent, in particular to its dielec-
tric constant E.
To simplify our explanation, we will consider two categories of acid in a solvent S, a neu-
tral acid molecule AH and a charged molecule BH'. Their respective protolysis reactions are
written:
AH+S aA-+SH'
(1.15)
BH++S~B+SH+

In the first case, reaction 1.15, which results in the formation of two charged entities, will
be favoured if the dielectric constant of the medium is large (for example E > 20). In the sec-
ond case, the number of charges in the medium remains constant: the physical action of the
medium is approximately cancelled by compensation. We can therefore easily understand
that by changing from a solvent of low dielectric constant to another solvent of high dielec-
tric constant, the reactions in the first category are much more likely than those in the sec-
ond. This explains why the classification order of the pKa values may be inverted in different
solvents.
We will now consider two acids B,H' and B,H' belonging to the homogeneous acid cat-

-
egory BH'. Their protolysis reactions in the solvent S are written:
B,H+ + S a B, + SH+ (1.16)
B,H'+ S B, + SH' (1.17)
Subtracting, term by term, these two equilibria, we obtain the new equilibrium:
B,H+ + B, e B, + B,H+ (1.18)
which does not depend on the solvent S.
22 Chapter 1 Overview on Acido-Basicity

The protolysis constant KBIIB2

of reaction 1.18 is equal to the ratio of the two protolysis
constants KB,and KB2of reactions 1.16 and 1.17:

We see that KB1,B2, which represents the relative acid strength of B,Ht with respect to the
base B,, is independent of the solvent S. Consequently, the differences ApK, of pK, between
various acid-base pairs BH'IB remain unchanged, irrespective of the solvents. This is only
true for a homogeneous category of acids (the category AHIA-, for example, or the category
BH+/B), but it is no longer true for a ApK, between two acid-base pairs belonging to differ-
ent categories. This is shown in figure 1.2, which compares the acidity scales obtained
respectively with water and methanol as reference solvents.

a. b.
A
- 12.4
11.g - hypochlorous
ethylamine

10.6
ethylamine
10.5 -
ammonia
(C2H5NH2)
9
ammonia
(HCIO) - 8.4
(NH40H) hypochlorous hydrofluoric
7.5 7.3 -
hydroxylamine

6
hydroxylamine - 5.6
(NH2OH) hydriodic

3.5
hydrofluoric -3
2.7 - nitric
(CH3CONH2) (HF) acetamide
acetamide
1.4 1.5 -
urea
0.7
hydriodic
_ _ _ _ _ _ _ _ 0.2
__ _.
urea

-2
nitric
(HNO3)

Fig. 1.2 [27]

Acidity scales. a. In water. b. In methanol. For each scale, the acids BH' are
positioned on the left and the acids A H on the right.
 Chapter 1 Overview on Acido-Basicity 23

Figure 1.3 shows that acids impossible to detect in water (levelling to pK, < 0) can be dis-
criminated in acetic acid, ethyl ether or benzene. Symmetrically, bases of pK, much greater
than 14 can be discriminated in ethyl alcohol, liquid ammonia, ethyl ether or benzene.
The above clearly demonstrates, if any further proof were needed, that all acidity scales
are relative scales. By no longer considering water as absolute reference, the Brransted-
Lowry theory admits that there is no point of universal neutrality and that the acidity and
basicity strengths vary in opposite directions along a continuum.

Water
Ethyl alcohol
Acetic acid
Formic acid
Liquid ammonia
Sulphuric acid
Ethyl ether
Benzene

Fig. 1.3 [4, 291

Ranges of pK, measurable in various solvents (the pK, values are reduced to
the reference medium, i.e. water).

1.2.2.9 Limits of the Brsnsted-Lowry Theory

In many respects, the Brransted-Lowry theory is much better than Arrhenius's theory, espe-
cially since it applies to various media including the gaseous phase, i.e. reactions in which
the ions are not necessarily solvated. It is not general enough, however. All chemical
processes not involving a proton and the protolysis phenomenon are excluded from the cat-
egory of acid-base reactions. Substances such as SO,, SO, and COz, for example, which do
not contain hydrogen but which have nevertheless been recognised for many years as acid
molecules, are not considered as acids.

1.2.3 The Lewis or Electronic Theory [2-4,30]

1.2.3.1 Definitions
With Lewis (1923) the idea emerged that there was too much emphasis on ions in
Arrhenius's theory and that the definition of an acid-base pair must not be restricted to sub-
stances containing protons. Lewis redefined a base as being a substance containing a free
24 Chapter I Overview on Acido-Basicity

electron pair which can be used to complete the incomplete outer electron shell of an acid
atom or molecule. Symmetrically, an acid is an acceptor of an electron pair which it uses to
complete its own valence ring in order to adopt a stable electron configuration. He therefore
proposed the following new definition which characterises the acido-basic interactions no
longer in terms of proton exchange but on the basis of a redistribution of the valence elec-
trons of the compounds: an acid-base reaction is a neutralisation which consists of com-
pleting the electron configuration of the acceptor (acid) with a free pair of electrons from a
donor (base), so that it takes a stable electron configuration, that of a rare gas. The two main
stable electron configurations are as follows: 2 (for He) and 8 (for Ne, Ar, Kr and Xe). The
product of the acid-base reaction is called, depending on the case: salt, adduct, coordination
complex, molecular complex, charge transfer compound, complex ion, etc. The bond formed
in the adduct is not only electrostatic but can be, and often is, covalent.
There are numerous known Lewis acids and bases, including for example:
- acids: proton H', SO,, SO,, COz, BCI,, SnCI,, Ag', etc. ;
- bases: OH-, I-, Br- , CI-, S2-, NH,, trimethylamine, pyridine, ethers, etc.
It is worth pointing out that the free proton Hf is the strongest Lewis acid.
The Lewis definition includes the reactions which occur in widely differing media: aqueous
and non-aqueous solvents, gaseous phase, solid surface. Amongst the solvents, the electron
theory accepts three classes: inert solvents such as benzene, ionising solvents such as water and
lastly reactive, non-ionising solvents such as pyridine and ethyl ether. The range of possible
acid-base reactions is therefore considerably wider than that of the Br~nsted-Lowrytheory.
However, it took over fifteen years before this theory, a radical change compared with the
previous ideas, was widely accepted by the scientific community, probably because it was
largely based on the covalent bond and because the theory of this bond, developed by Lewis
in 1916, was still very young and far from being unanimously shared.

1.2.3.2 The Various Categories of Acid-Base Reactions According to Lewis

The acid-base reaction according to Lewis is a heterolytic reaction which can be considered
as the breaking and formation of a covalent bond where the two electrons are donated or
accepted by only one of the partners. Acid-base processes according to Lewis can all be
described by the following, very general relation between the acids A and A' and the bases
:B and :B' [32, 331:
A:B' + A':B w A:B + A':B' (1.19)
where the bold colons (:) indicate an electron pair.
There are several possibilities:
When the partners A' and :B' are absent, the reaction is a process of addition or neutrali-
sation of the two reactants A and :B to form the adduct A:B; for example, in the case of neu-
tral entities:
..
F H
.. F H .. ..
F:B
.. + : N..: H + .. ..
F:B:N:H
F H F H
 Chapter I Overview on Acido-Basicity 25

c1
.. c..
1
or : Cl:B+:NCgHg
.. + C1:B:NC5H5
..
c1 CI
where B represents boron.
In most coordination compounds, the acceptor is a positive ion:
2NH3 + Ag+ + [H3N :Ag :NH,]'
4NH3 + Pt2+-+ [Pt(NH3),]*'
Generally, reactions of this type, whose inverse is the heterolysis of the A:B bond of the
adduct, are rare, occumng in particular in gaseous phase or in weakly acid or basic solvents
(for example hexane) which do not significantly coordinate the base or the acid [32, 331.
When one of the partners A' or :B' in reaction 1.19 is absent, then a shift or substitution
reaction occurs. Two sub-categories can be identified:
- Nucleophilic substitution
Base :B displaces base :B' from molecule A:B' to form the adduct A:B, base :B' released
taking with it the 2 electrons of the A:B' bond:
:B + A:B' -+ A:B + :B'
such as, for example:
.. ..
..
lX:]+ R:CI: + : X..: R + [ :: ]
:Cl:

where: X- = I-, Br-, CN-, OH-. ..

and R + = H', CHf, CH3CO+...
This type of reaction includes the special case of the proton:

.. ..
:O:H + : C l : H
H
+ [ H
H:O:H ]+[:.:1
Nucleophilic substitutions are the most frequently encountered Lewis acid-base reactions.
Electrophilic substitutions discussed below are less frequently encountered [32, 331.
- Electrophilic substitution
An acid A attacks the bond of the molecule A':B to form the adduct A:B, thereby dis-
placing the acid A'. This reaction is equivalent to transferring an atom :B, with a com-
plete electron shell, from one acid to another:
A + A':B + A:B + A'
For example:
.. ..
.. c..1 :
:
.. .. c..1 ..
.. .. +
:CI:Al
..
:Cl:R -+ R+ t :C1 :A1 : CI :
.. .. ..
:c1:.. : c1:
..
 Next Page

26 Chapter I Overview on Acido-Basicity

Acid-base reactions involving the four partners of the general reaction 1.19 are known as
double shift or double substitution reactions. They include, in fact, the shift of both an acid
and a base.

1.2.3.3 Classification of Lewis Acids and Bases

By moving from the concept of proton transfer (Brsnsted-Lowry definition) to that of electron
pair transfer, Lewis helped give a much wider view of the finally very general phenomenon of
acidity and provide a definition which is still relevant today. It soon became clear, however, that
due to this generalisation it would be difficult to classify acids and bases. The initial difficulty
comes from the fact that there is no universal reference in the Lewis definition to make a clas-
sification, whereas in the Brsnsted-Lowry theory the acid-base pairs can be compared on the
basis of the proton transfer measured by the pK,, water solvent being chosen as reference.
In principle, the most satisfactory quantitative approach for acido-basicity is that based
on the measurement of reaction equilibrium constants AGO [32,33]. Unfortunately, the accu-
rate experimental determination of these constants is often difficult, and few results have
been obtained which are reliable enough to be used in practice. The reaction enthalpies may
possibly be used, but this solution is less satisfactory [32, 331. This second difficulty
explains why very few classification attempts based on the experimental measurements of
thermodynamic characteristics of acid-base reactions have been made.
Satchel1 [32, 331, who had appreciated these difficulties, proposed the following qualita-
tive classification of the acidity of compounds with general formula MX,, mainly based on
the electron configuration of the central atom M:
BX, > AIX, > FeX, > GaX, > SbX, > InX3 > SnX, > AsX, > ZnX, > HgX,
This classification is only an approximation, however, since the substituents X, mostly
halogens, may also affect the acidity of the compounds due to their inductive and steric
effects [32, 331. Other effects are also involved, for example the type of the basic partner
compound (electron state, steric effects, etc.).
Gutmann made a more quantitative attempt to classify the compounds donating electron
pairs (therefore basic), based on the values of their reaction enthalpies with SbCl,, used as
common acceptor [28,34]. The reaction carried out in dichloroethanecan be used to define a
donor number DN, where a value of 0 corresponds to the weakest donors: the hydrocarbons
and their halogenated derivatives. Pyridine and hexamethylphosphoramide (HMPA) are the
strongest donors with DN = 33.1 and 38.8 respectively, acetone and water are intermediate
with respectively DN = 17 and DN = 18.Amongst the other DN values which have been deter-
mined, we may mention nitrobenzene (DN = 4.4), acetic anhydride (DN = lO.S), sulpholane
(14.8), diethyl ether (DN = 19.2), THF (DN = 20), DMF (DN = 26.6) and DMSO (DN = 29.8).

1.2.3.4 Weaknesses of the Lewis Electronic Theory

Originally the Lewis theory had certain weak points, strongly attacked by his critics,
including:
- The halide ions X- form one of the Lewis bases categories. However, the classification
of the basicity of these ions is inverted depending on whether we consider their