acid–base reaction

acid–base reaction, a type of

TABLE OF CONTENTS
chemical process typified by the
exchange of one or more Introduction
hydrogen ions, H+, between Theoretical definitions of acids and
species that may be neutral bases
(molecules, such as water, H2O; Acid–base reactions
or acetic acid, CH3CO2H) or Acid–base equilibria

electrically charged (ions, such as Dissociation constants in aqueous

solution
ammonium, NH4+; hydroxide,
Selected values of acidity constants
OH−; or carbonate, CO32−). It

also includes analogous behaviour of

molecules and ions that are acidic but do
not donate hydrogen ions (aluminum
chloride, AlCl3, and the silver ion AG+).

sodium sulfate Acids are chemical compounds that show,

Sodium sulfate, also called Glauber's
in water solution, a sharp taste, a corrosive
salt, is, like other salts, the product of action on metals, and the ability to turn
an acid-base reaction.
certain blue vegetable dyes red. Bases are
chemical compounds that, in solution, are
soapy to the touch and turn red vegetable dyes blue. When mixed, acids and
bases neutralize one another and produce salts, substances with a salty taste and
none of the characteristic properties of either acids or bases.

The idea that some substances are acids whereas others are bases is almost as old
as chemistry, and the terms acid, base, and salt occur very early in the writings
of the medieval alchemists. Acids were probably the first of these to be
recognized, apparently because of their sour taste. The English word acid, the

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 French acide, the German Säure, and the Russian kislota are all derived from
words meaning sour (Latin acidus, German sauer, Old Norse sūur, and Russian
kisly). Other properties associated at an early date with acids were their solvent,
or corrosive, action; their effect on vegetable dyes; and the effervescence
resulting when they were applied to chalk (production of bubbles of carbon
dioxide gas). Bases (or alkalies) were characterized mainly by their ability to
neutralize acids and form salts, the latter being typified rather loosely as
crystalline substances soluble in water and having a saline taste.

In spite of their imprecise nature, these ideas served to correlate a considerable

range of qualitative observations, and many of the commonest chemical
materials that early chemists encountered could be classified as acids
(hydrochloric, sulfuric, nitric, and carbonic acids), bases (soda, potash, lime,
ammonia), or salts (common salt, sal ammoniac, saltpetre, alum, borax). The
absence of any apparent physical basis for the phenomena concerned made it
difficult to make quantitative progress in understanding acid–base behaviour, but
the ability of a fixed quantity of acid to neutralize a fixed quantity of base was
one of the earliest examples of chemical equivalence: the idea that a certain
measure of one substance is in some chemical sense equal to a different amount
of a second substance. In addition, it was found quite early that one acid could be
displaced from a salt with another acid, and this made it possible to arrange acids
in an approximate order of strength. It also soon became clear that many of these
displacements could take place in either direction according to experimental
conditions. This phenomenon suggested that acid–base reactions are reversible—
that is, that the products of the reaction can interact to regenerate the starting
material. It also introduced the concept of equilibrium to acid–base chemistry:
this concept states that reversible chemical reactions reach a point of balance, or
equilibrium, at which the starting materials and the products are each regenerated
by one of the two reactions as rapidly as they are consumed by the other.

Apart from their theoretical interest, acids and bases play a large part in industrial
chemistry and in everyday life. Sulfuric acid and sodium hydroxide are among

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 the products manufactured in largest amounts by the chemical industry, and a
large percentage of chemical processes involve acids or bases as reactants or as
catalysts. Almost every biological chemical process is closely bound up with
acid–base equilibria in the cell, or in the organism as a whole, and the acidity or
alkalinity of the soil and water are of great importance for the plants or animals
living in them. Both the ideas and the terminology of acid–base chemistry have
permeated daily life, and the term salt is especially common.

Theoretical definitions of acids and bases

Hydrogen and hydroxide ions
The first attempt at a theoretical interpretation of acid behaviour was made by
Antoine-Laurent Lavoisier at the end of the 18th century. Lavoisier supposed that
all acids must contain oxygen, and this idea was incorporated in the names used
for this element in the various languages; the English oxygen, from the Greek
oxys (sour) and genna (production); the German Sauerstoff, literally acid
material; and the Russian kislorod, from kislota (acid). Following the discovery
that hydrochloric acid contained no oxygen, Sir Humphry Davy about 1815 first
recognized that the key element in acids was hydrogen. Not all substances that
contain hydrogen, however, are acids, and the first really satisfactory definition
of an acid was given by Justus von Liebig of Germany in 1838. According to
Liebig, an acid is a compound containing hydrogen in a form in which it can be
replaced by a metal. This definition held the field for about 50 years and is still
considered essentially correct, though somewhat outmoded. At the time of
Liebig’s proposal, bases were still regarded solely as substances that neutralized
acids with the production of salts, and nothing was known about the
constitutional features of bases that enabled them to do this.

The whole subject of acid–base chemistry acquired a new look and a quantitative
aspect with the advent of the electrolytic dissociation theory propounded by
Wilhelm Ostwald and Svante August Arrhenius (both Nobel laureates) in the
1880s. The principal feature of this theory is that certain compounds, called

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 electrolytes, dissociate in solution to give ions. With the development of this
theory it was realized that acids are merely those hydrogen compounds that give
rise to hydrogen ions (H+) in aqueous solution. It was also realized at that time
that there is a correspondence between the degree of acidity of a solution (as
shown by effects on vegetable dyes and other properties) and the concentration
of hydrogen ions in the solution. Correspondingly, basic (or alkaline) properties
could then be associated with the presence of hydroxide ions (OH−) in aqueous
solution, and the neutralization of acids by bases could be explained in terms of
the reaction of these two ions to give the neutral molecule water (H+ + OH− →
H2O). This led naturally to the simple definition that acids and bases are
substances that give rise, respectively, to hydrogen and hydroxide ions in
aqueous solution. This definition was generally accepted for the next 30 or 40
years. In purely qualitative terms, it does not offer many advantages over
Liebig’s definition of acids, but it does provide a satisfactory definition for bases.

Nevertheless, there is a great advantage in the definition of acids and bases in

terms of hydrogen and hydroxide ions, and this advantage lies in its quantitative
aspects. Because the concentrations of hydrogen and hydroxide ions in solution
can be measured, notably by determining the electrical conductivity of the
solution (its ability to carry an electrical current), a quantitative measure of the
acidity or alkalinity of the solution is provided. Moreover, the equations
developed to express the relationships between the various components of
reversible reactions can be applied to acid and base dissociations to give definite
values, called dissociation constants. These constants can be used to characterize
the relative strengths (degrees of dissociation) of acids and bases and, for this
reason, supersede earlier semiquantitative estimates of acid or base strength. As a
result of this approach, a satisfactory quantitative description was given at an
early date of a large mass of experimental observations, a description that
remains essentially unaffected by later developments in definitions of acid–base
reactions.

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 The success of these quantitative developments, however, unfortunately helped
to conceal some ambiguities and logical inconsistencies in the qualitative
definitions of acids and bases in terms of the production of hydrogen and
hydroxide ions, respectively. For example, it was not clear whether a substance
like anhydrous hydrogen chloride, which would not conduct electricity, should be
regarded as an acid or whether it should be considered an acid only after it had
come in contact with water. A modified definition of bases also seemed to be
required that would be applicable to nonaqueous solutions, in which the anion
(negatively charged ion) produced is not the hydroxide ion, as is the case in
water, but varies from solvent to solvent, the methoxide ion (CH3O−) acting as
the basic anion in methanol (CH3OH), for example, and the amide ion (NH2−)
playing the same role in liquid ammonia (NH3). Even with acids the solvent is
involved, since there is much evidence to show that the so-called hydrogen ion in
solution does not exist as H+ but always contains at least one molecule of
solvent, as H3O+ in water, CH3OH2+ in methanol, and NH4+ in liquid ammonia.
These considerations led to the development of definitions of acids and bases that
depended on the solvent (see below Alternative definitions). In spite of this
change, however, the difficulty still remained that typical acid–base properties,
such as neutralization, indicator (vegetable dye) effects, and catalysis, often took
place in solvents such as benzene or chloroform in which free ions could barely
be detected at all (by conductivity measurements). Even for aqueous solutions a
particular ambiguity arises in the definition of bases, some of which (for
example, metallic hydroxides) contain a hydroxyl group, whereas others (such as
amines) do not. The latter produce hydroxide ions in solution by reacting with
water molecules.

The Brønsted–Lowry definition

In order to resolve the various difficulties in the hydrogen–hydroxide ion
definitions of acids and bases, a new, more generalized definition was proposed
in 1923 almost simultaneously by J.M. Brønsted and T.M. Lowry. Although the

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 pursuit of exact verbal definitions of qualitative concepts is usually not profitable
in physical science, the Brønsted–Lowry definition of acids and bases has had
far-reaching consequences in the understanding of a wide range of phenomena
and in the stimulation of much experimental work. The definition is as follows:
an acid is a species having a tendency to lose a proton, and a base is a species
having a tendency to gain a proton. The term proton means the species H+ (the
nucleus of the hydrogen atom) rather than the actual hydrogen ions that occur in
various solutions; the definition is thus independent of the solvent. The use of the
word species rather than substance or molecule implies that the terms acid and
base are not restricted to uncharged molecules but apply also to positively or
negatively charged ions. This extension is one of the important features of the
Brønsted–Lowry definition. It can be summarized by the equation A ⇄ B + H+,
in which A and B together are a conjugate acid–base pair. In such a pair A must
obviously have one more positive charge (or one less negative charge) than B,
but there is no other restriction on the sign or magnitude of the charges.

Several examples of conjugate acid–base pairs are given in the table.

Examples of conjugate acid-base pairs

acid base

acetic acid, CH3CO2H acetate ion, CH3CO2−

bisulfate ion, HSO4− sulfate ion, SO42−

ammonium ion, NH4+ ammonia, NH3

ammonia, NH3 amide ion, NH2−

water, H2O hydroxide ion, OH−

hydronium (oxonium) ion, H3O+ water, H2O

A number of points about the Brønsted–Lowry definition should be emphasized:

1. As mentioned above, this definition is independent of the solvent. The ions

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 derived from the solvent (H3O+ and OH− in water and NH4+ and NH2− in liquid
ammonia) are not accorded any special status but appear as examples of acids or
bases in terms of the general definition. On the other hand, of course, they will be
particularly important species for reactions in the solvent to which they relate.

2. In addition to the familiar molecular acids, two classes of ionic acids emerge
from the new definition. The first comprises anions derived from acids
containing more than one acidic hydrogen—e.g., the bisulfate ion (HSO4−) and
primary and secondary phosphate ions (H2PO4− and HPO42−) derived from
phosphoric acid (H3PO4). The second and more interesting class consists of
positively charged ions (cations), such as the ammonium ion (NH4+), which can
be derived by the addition of a proton to a molecular base, in this case ammonia
(NH3). The hydronium ion (H3O+), which is the hydrogen ion in aqueous
solution, also belongs to this class. The charge of these ionic acids, of course,
always must be balanced by ions of opposite charges, but these oppositely
charged ions usually are irrelevant to the acid–base properties of the system. For
example, if sodium bisulfate (Na+HSO4−) or ammonium chloride (NH4+Cl−) is
used as an acid, the sodium ion (Na+) and the chloride ion (Cl−) contribute
nothing to the acidic properties and could equally well be replaced by other ions,
such as potassium (K+) and perchlorate (ClO4−), respectively.

3. Molecules such as ammonia and organic amines are bases by virtue of their
tendency to accept a proton. With metallic hydroxides such as sodium hydroxide,
on the other hand, the basic properties are due to the hydroxide ion itself, the
sodium ion serving merely to preserve electrical neutrality. Moreover, not only
the hydroxide ion but also the anions of other weak acids (for example, the
acetate ion) must be classed as bases because of their tendency to reform the acid
by accepting a proton. Formally, the anion of any acid might be regarded as a
base, but for the anion of a very strong acid (the chloride ion, for example) the
tendency to accept a proton is so weak that its basic properties are insignificant

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 and it is inappropriate to describe it as a base. Similarly, all hydrogen compounds
could formally be defined as acids, but in many of them (for example, most
hydrocarbons, such as methane, CH4) the tendency to lose a proton is so small
that the term acid would not normally be applied to them.

4. Some species, including molecules as well as ions, possess both acidic and
basic properties; such materials are said to be amphoteric. Both water and
ammonia are amphoteric, a situation that can be represented by the schemes
H3O+–H2O–OH− and NH4+–NH3–NH2−. Another example is the secondary
phosphate ion, HPO42−, which can either lose or accept a proton, according to
− − − −
the following equations: HPO42 ⇄ PO43 + H+ and HPO42 + H+ ⇄ H2PO4 .
The amphoteric properties of water are particularly important in determining its
properties as a solvent for acid–base reactions.

5. The equation A ⇄ B + H+, used in the Brønsted–Lowry definition, does not

represent a reaction that can be observed in practice, since the free proton, H+,
can be observed only in gaseous systems at low pressures. In solution, the proton
always is attached to some other species, commonly a solvent molecule. Thus in
water the ion H3O+ consists of a proton bound to a water molecule. For this
reason all observable acid–base reactions in solution are combined in pairs, with
the result that they are of the form A1 + B2 ⇄ B1 + A2. The fact that the process
A ⇄ B + H+ cannot be observed does not imply any serious inadequacy of the
definition. A similar situation exists with the definitions of oxidizing and
reducing agents, which are defined respectively as species having a tendency to
gain or lose electrons, even though one of these reactions never occurs alone and
free electrons are never detected in solution (any more than free protons are).

Alternative definitions
Although the Brønsted–Lowry concept of acids and bases as donors and
acceptors of protons is still the most generally accepted one, other definitions are

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 often encountered. Certain of these are adapted for special situations only, but the
most important of these other definitions is in some respects more general than
the Brønsted–Lowry definition. This definition was first proposed by the
American chemist Gilbert N. Lewis in 1923.

According to Lewis, an acid is a species that can accept an electron pair from a
base with the formation of a chemical bond composed of a shared electron pair
(covalent bond). This classification includes as bases the same species covered
by the Brønsted–Lowry definition, since a molecule or ion that can accept a
proton does so because it has one or more unshared pairs of electrons, and
therefore it also can combine with electron acceptors other than the proton. On
the other hand, the typical Lewis acids need not (and usually do not) contain
protons, being species with outer electron shells that are capable of expansion,
such as boron trifluoride (BF3), sulfur trioxide (SO3), and silver ion (Ag+).
Lewis originally based his ideas on the experimental fact that these nonprotonic
acids often exhibit the properties regarded as typical of acids, such as
neutralization of bases, action on indicators, and catalysis. Such substances often
are electron acceptors, but this is not always the case; carbon dioxide (CO2) and
nitrogen pentoxide (N2O5), for example, contain completed octets of electrons
and, according to usual valence theory, cannot accept any more. In addition,
hydrogen-containing substances that have always been regarded as acids (acetic
acid, for example) are not obviously electron acceptors, being rather adducts of
the proton (a true Lewis acid) and a base such as the acetate ion. They can only
be brought logically into the Lewis scheme by appealing to the fact that the
reaction between a proton acid, which may be designated as XH, and a base,
denoted by B, passes through an intermediate hydrogen-bonded state, X-H…B
(in which the dotted line indicates a hydrogen bond, a relatively weak secondary
attractive force).

Numerous lengthy polemical exchanges have taken place regarding the relative
merits of the Brønsted–Lowry and Lewis definitions. The difference is

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 essentially one of nomenclature and has little scientific content. In the remainder
of this article the term acid is used to denote a proton donor (following the
Brønsted–Lowry terminology), whereas the term Lewis acid is employed
exclusively to refer to electron-pair acceptors. This choice is based partly on the
logical difficulties mentioned in the last paragraph and partly on the fact (see
below Acid–base equilibria) that the quantitative description of acid–base
reactions is much simpler when it is confined to proton acids. It also represents
the commonest usage of the terms.

The definition of Lewis acids and bases in terms of the gain or loss of electrons
should not be confused with the definition of oxidizing and reducing agents in
similar terms. In oxidation–reduction reactions one or more electrons are
transferred completely from the reducing agent to the oxidizing agent, whereas in
a Lewis acid–base reaction an electron pair on the base is used to form a covalent
link with the acid.

Certain other acid–base definitions have been based upon reactions occurring in
specific solvent systems. For proton acids in amphoteric solvents these are
equivalent to the Brønsted–Lowry definition. It is sometimes convenient to have
general terms for the cation and anion derived from the solvent molecule by the
addition and removal of a proton, respectively. The terms lyonium and lyate ions
are occasionally used in this way. In water, the lyonium and lyate ions are H3O+
and OH−; in ethanol, C2H5OH2+ and C2H5O−; and in liquid ammonia, NH4+
and NH2−. For a given solvent, an acid can then be defined as a substance that
increases the lyonium ion concentration (and correspondingly decreases the lyate
ion concentration), whereas a base increases the lyate ion concentration (and
decreases the lyonium ion concentration). This kind of definition, to be sure,
really does not add anything to the concept of acids and bases as proton donors
and proton acceptors.

The idea that an acid is a solute that gives rise to cations characteristic of the

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 solvent and that a base is a solute that gives rise to anions characteristic of the
solvent has sometimes been extended to solvents where no protons are involved
at all—for example, liquid sulfur dioxide, SO2. In this example, the solvent is
supposed to ionize according to the equation 2SO2 ⇄ SO2+ + SO32−. Thionyl
chloride, regarded as SO2+ + 2Cl−, then can be considered an acid, and
potassium sulfite, 2K+ + SO32−, can be considered a base. The species SO2+ and
SO32− can certainly be regarded as Lewis acids and bases, but it is doubtful that
they exist to any appreciable extent in liquid sulfur dioxide, a situation that
makes the discussion somewhat artificial. Although this view of acids and bases
has been useful in stimulating work in unusual types of solvent (for example, in
carbonyl chloride, selenium oxychloride, antimony trichloride, and hydrogen
cyanide), it has not met with general acceptance.

Acid–base reactions
Proton-transfers
As already mentioned (The Brønsted–Lowry definition), the reaction expressed
by the Brønsted–Lowry definition, A ⇄ B + H+, does not actually occur in any
solution processes. This is because H+, the bare proton, has an enormous
tendency to add to almost all chemical species and cannot exist in any detectable
concentrations except in a high vacuum. Apart from any specific chemical
interaction, the very small size of the proton (about 10−15 metre) means that it
exerts an extremely powerful electric field, which will polarize and therefore
attract any molecule or ion it comes into contact with. It has been estimated that
the dissociation of 19 grams of the hydronium ion H3O+ to give 1 gram of
protons and 18 grams of water would require the expenditure of about 1,200,000
joules (290,000 calories) of energy, and thus it is an extremely unlikely process
indeed.

Typical acid–base reactions may be thought of as the combination of two

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 reaction schemes, A1 ⇄ B1 + H+ and H+ + B2 ⇄ A2, leading to the combined
form A1 + B2 ⇄ B1 + A2. This represents a proton-transfer reaction from A1 to
B2, producing B1 and A2. A large number of reactions in solution, often referred
to under a variety of names, can be represented in this way. This is illustrated by
the following examples, in each of which the species are written in the order A1,
B2, B1, A2.

Dissociation of molecular acids in water

In this instance, water acts as a base. The equation for the dissociation of acetic
acid, for example, is CH3CO2H + H2O ⇄ CH3CO2− + H3O+.

Dissociation of bases in water

In this case, the water molecule acts as an acid and adds a proton to the base. An
example, using ammonia as the base, is H2O + NH3 ⇄ OH− + NH4+. Older
formulations would have written the left-hand side of the equation as ammonium
hydroxide, NH4OH, but it is not now believed that this species exists, except as a
weak, hydrogen-bonded complex.

Dissociation of acids and bases in nonaqueous solvents

These situations are entirely analogous to the comparable reactions in water. For
example, the dissociation of acetic acid in methanol may be written as
CH3CO2H + CH3OH ⇄ CH3CO2− + CH3OH and the dissociation of ammonia
in the same solvent as CH3OH + NH3 ⇄ CH3O− + NH4+.

Self-dissociation of amphoteric solvents

In this case, one solvent molecule acts as an acid and another as a base. Self-
dissociation of water and liquid ammonia may be given as examples:

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 Neutralization
For a strong acid and a strong base in water, the neutralization reaction is
between hydrogen and hydroxide ions—i.e., H3O+ + OH− ⇄ 2H2O. For a weak
acid and a weak base, neutralization is more appropriately considered to involve
direct proton transfer from the acid to the base. For example, the neutralization of
acetic acid by ammonia may be written as CH3CO2H + NH3 → CH3CO2− +
NH4+. This equation does not involve the solvent; it therefore also represents the
process of neutralization in an inert solvent, such as benzene, or in the complete
absence of a solvent. (If one of the reactants is present in large excess, the
reaction is more appropriately described as the dissociation of acetic acid in
liquid ammonia or of ammonia in glacial acetic acid.)

Hydrolysis of salts
Many salts give aqueous solutions with acidic or basic properties. This is termed
hydrolysis, and the explanation of hydrolysis reactions in classical acid–base
terms was somewhat involved. In terms of the Brønsted–Lowry concept,
however, hydrolysis appears to be a natural consequence of the acidic properties
of cations derived from weak bases and the basic properties of anions derived
from weak acids. For example, hydrolysis of aqueous solutions of ammonium
chloride and of sodium acetate is represented by the following equations:

The sodium and chloride ions take no part in the reaction and could equally well
be omitted from the equations.

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 The acidity of the solution represented by the first equation is due to the presence
of the hydronium ion (H3O+), and the basicity of the second comes from the
hydroxide ion (OH−). The reverse reactions simply represent, respectively, the
neutralization of aqueous ammonia by a strong acid and of aqueous acetic acid
by a strong base.

A superficially different type of hydrolysis occurs in aqueous solutions of salts of

some metals, especially those giving multiply charged cations. For example,
aluminum, ferric, and chromic salts all give aqueous solutions that are acidic.
This behaviour also can be interpreted in terms of proton-transfer reactions if it is
remembered that the ions involved are strongly hydrated in solution. In a solution
of an aluminum salt, for instance, a proton is transferred from one of the water
molecules in the hydration shell to a molecule of solvent water. The resulting
hydronium ion (H3O+) accounts for the acidity of the solution:

Reactions of Lewis acids

In the reaction of a Lewis acid with a base the essential process is the formation
of an adduct in which the two species are joined by a covalent bond; proton
transfers are not normally involved. If both the Lewis acid and base are
uncharged, the resulting bond is termed semipolar or coordinate, as in the
reaction of boron trifluoride with ammonia:

Frequently, however, either or both species bears a charge (most commonly a

positive charge on the acid or a negative charge on the base), and the location of
charges within the adduct often depends upon the theoretical interpretation of the
valences involved. Examples are:

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 In another common type of process, one acid or base in an adduct is replaced by
another:

In fact, reactions such as the simple adduct formations above often are
formulated more correctly as replacements. For example, if the reaction of boron
trifluoride with ammonia is carried out in ether as a solvent, it becomes a
replacement reaction:

Similarly, the reaction of silver ions with ammonia in aqueous solution is better
written as a replacement reaction:

Furthermore, if most covalent molecules are regarded as adducts of (often

hypothetical) Lewis acids and bases, an enormous number of reactions can be
formulated in the same way. To take a single example, the reaction of methyl
chloride with hydroxide ion to give methanol and chloride ion (usually written as
CH3Cl + OH− → CH3OH + Cl−) can be reformulated as replacement of a base in
a Lewis acid–base adduct, as follows: (adduct of CH3+ and Cl−) + OH− →

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 (adduct of CH3+ and OH−) + Cl−. Opinions differ as to the usefulness of this
extremely generalized extension of the Lewis acid–base-adduct concept.

The reactions of anhydrous oxides (usually solid or molten) to give salts may be
regarded as examples of Lewis acid–base-adduct formation. For example, in the
reaction of calcium oxide with silica to give calcium silicate, the calcium ions
play no essential part in the process, which may be considered therefore to be
adduct formation between silica as the acid and oxide ion as the base:

A great deal of the chemistry of molten-oxide systems can be represented in this

way, or in terms of the replacement of one acid by another in an adduct.

Acid–base catalysis
Acids (including Lewis acids) and bases act as powerful catalysts for a great
variety of chemical reactions, in the laboratory, in industry, and in processes
occurring in nature. Historically, catalytic action was regarded as one of the
essential characteristics of acids, and the parallel occurrence of catalytic action
and electrical conductivity was one of the compelling pieces of evidence in
establishing the theory of electrolytic dissociation as the basis of acid–base
behaviour at the end of the 19th century.

Acid–base catalysis was originally thought of in terms of a mysterious influence

of the acid or base, but it is now generally believed to involve an actual acid–
base reaction between the catalyst and the reacting substance, termed the
substrate, with the catalyst being regenerated at a later stage of the reaction.
Moreover, knowledge of reaction mechanisms is now sufficient to suggest
detailed sequences of reactions for many acid- or base-catalysis reactions, most
of these sequences being at least plausible and in many instances well
established.

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 In most acid–base reactions the addition or removal of a proton does not bring
about any drastic change in the structure of the molecule or in its stability or
reactivity. It is a characteristic of reactions catalyzed by acids or bases, however,
that the addition or removal of a proton either makes the substrate unstable, so
that it decomposes or rearranges, or that it causes the substrate to become
reactive toward some other species present in the system. In cases of
rearrangement, the regeneration of the catalyst often involves the removal or
addition of a proton at a site other than that at which the initial addition or
removal took place. It is not necessary that the substrate in an acid- or base-
catalyzed reaction should itself have marked acid–base properties, since even a
very small extent of initial acid–base reaction may be enough to bring about the
subsequent change.

Instances of acid–base catalysis are numerous indeed; a few examples are given
here, as follows:

Isomerization of olefins, acid-catalyzed

Unsaturated compounds frequently rearrange reversibly under the influence of
acids to give products in which the double bond occurs in a new location. The
interconversion of 2-butene and 1-butene is shown here:

Reversible dehydration of alcohols, acid-catalyzed. Under the influence of acids,

alcohols generally undergo loss of water to give olefinic products. The
dehydration of ethanol to ethylene occurs as follows:

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 Keto–enol tautomerism, acid- and base-catalyzed
Acids and bases both bring about the establishment of an equilibrium between
ketones (or aldehydes) and their enol forms, which contain a hydroxyl group
directly attached to a doubly bonded carbon atom:

The interconversion between the two forms is called keto–enol tautomerism. The
reaction cannot always be observed directly, since the enol form may not reach
measurable concentrations, even at equilibrium, but the highly active enol may
be detected by its reaction with various reagents, notably the halogens (bromine,
for example). Keto–enol tautomerization of acetone can be brought about by acid
or base catalysis, as follows:

Aldol condensation, base-catalyzed

Self-condensation of aldehydes, the so-called aldol condensation, occurs readily,
when catalyzed by bases, to give β-hydroxy aldehydes. The prototype of this
reaction is the conversion of acetaldehyde to β-hydroxybutyraldehyde, or aldol.
The first step of this reaction is the production of an enolate ion (as in formation
of the keto–enol tautomeric mixture), but this anion then reacts with a second

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 molecule of acetaldehyde to give the product as shown below:

These examples illustrate the importance of acid–base catalysis in organic

reactions. The equations have been written in terms of H3O+ and OH− as the acid
and base catalysts, respectively, and these are certainly the most important
catalysts in aqueous solution. For many of these reactions (especially
isomerization of olefins and dehydration of alcohols), there is ample evidence
that other acids or bases also can act as catalysts. This behaviour is known as
general acid–base catalysis. It appears particularly clearly in inert solvents such
as benzene, in which catalysis by molecular acids and bases is frequently
observed despite the absence of detectable quantities of ions derived from the
solvent. Acidic groups, such as sulfonic acid (−SO3H) and carboxylic acid
groups (−CO2H), attached to a solid molecular framework (as in some ion
exchange resins) also act as heterogeneous catalysts for many chemical reactions.

The above examples show that proton-transfer processes can play a specific part
in reaction mechanisms and, in these and similar instances, it is doubtful whether
any uncatalyzed or spontaneous reaction of the same type can take place.
Apparent evidence to the contrary can usually be explained by catalysis by
solvent molecules or by adventitious acidic or basic impurities.

Lewis acids can exert a catalytic effect in two different ways. In the first of these
they interact with hydrogen-containing compounds present in the system to assist
the release of a proton to the substrate. For example, the polymerization of
olefins by Lewis acids, such as boron trifluoride (BF3), aluminum chloride
(AlCl3), and titanium tetrachloride (TiCl4), is believed to be caused by their
interaction with proton acids (for example, traces of water) and the olefin to give

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 a carbonium ion, which then reacts further with more olefin:

In the second mode of action, the Lewis acid acts directly on the substrate, and
by withdrawing electrons converts it into a reactive form. A typical example is
the action of catalysts like aluminum chloride on alkyl halides to produce
carbonium ions: RCl + AlCl3 → R+ + [AlCl4]−. The carbonium ion can then
react further with other substances, for example, aromatic hydrocarbons. The
same type of catalysis probably occurs with many solid oxide catalysts (for
example, aluminosilicates), although it is often difficult to decide whether the
catalytic action of these materials is due to centres with a deficiency of electrons
or to acidic hydroxyl groups.

Acid–base equilibria
Certain general principles apply to any solvent with both acidic and basic
properties—for example, water, alcohols, ammonia, amines, and acetic acid.
Denoting the solvent molecule by SH, proton transfer can give rise to the ions
SH2+ and S−, sometimes called lyonium and lyate ions, respectively (see above).
In the pure solvent these are the only ions present, and they must be present in
equal concentrations to preserve electrical neutrality. The equilibrium involved,
therefore, is as follows: 2SH ⇄ SH2+ + S−. The equilibrium constant (Ks′) for
this reaction (the mathematical quantity that expresses the relationships between
the concentrations of the various species present at equilibrium) would normally
be given by the equation Ks′ = [SH2+] [S−]/[SH]2, in which the square brackets
denote the concentrations of the species within the brackets. In a given solvent,
however, the concentration of the solvent, [SH], is a large and constant quantity,
and it is therefore usual to eliminate this term and express the self-dissociation of
the solvent by the equation Ks = [SH2+][S−]. In this equation, Ks is termed the

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 ion product or the autoprotolysis constant of the solvent. The concentrations are
usually expressed in moles per litre, a mole being the molecular weight of the
compound in grams. Since a solvent that is a good proton donor is normally a
poor proton acceptor, and vice versa, the degree of ionization is generally low
and Ks is usually a small quantity. It is about 10−14 for water at ordinary
temperatures, and one of the largest Ks values known is 1.7 × 10−4 for 100
percent sulfuric acid. The above equation applies not only to the pure solvent, but
also (with the same value of Ks) to any dilute solutions of acids, bases, or salts in
the solvent in question. In these solutions [SH2+] and [S−] need not be equal,
since the condition of electrical neutrality involves the concentration of other
ions as well, and it is obvious from the equation that a high value of [SH2+] must
imply a low value of [S−] and vice versa.

If an acid A is added to the solvent SH it will be at least partly converted into the
conjugate base B according to the reaction A + SH ⇄ B + SH2+, which would be
characterized formally by an equilibrium constant [B][SH2+]/[A] [SH]. Again,
however, it is usual to omit the term for the constant concentration of the solvent,
[SH], from this expression, and to define a constant Ka by the equation

which is known as the dissociation constant of the acid A in the

solvent SH. Any acid–base reaction A1 + B2 ⇄ B1 + A2 will proceed from left
to right almost completely if A1 is a much stronger acid than A2. It is a natural
extension of this idea to use the equilibrium constant as a measure of the strength
of A1 relative to A2. The dissociation constant is thus (apart from the constant
factor [SH], which has been omitted) a measure of the acid strength of A relative
to that of the lyonium ion SH2+.

In some instances reaction goes so completely from left to right that it is not
possible to measure the equilibrium constant. A is said then to be a strong acid in
the solvent SH; similarly, acids with readily measurable dissociation constants

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 (in practice less than about 0.1) are known as weak acids.

Similar considerations apply to solutions of bases. The reaction involved in this

case is SH + B ⇄ S− + A, and the equilibrium constant Kb defined by

is known as the dissociation constant of the base B. Apart from the omitted
constant factor [SH], Kb represents the basic strength of B relative to that of the
lyate ion S−. Bases are termed strong and weak in the same way that acids are.

The values of Ka and Kb for a conjugate acid–base pair A–B in a given solvent
are not independent, since consideration of the dissociation constants of the
solvent, acid, and base show that KaKb = [SH2+][S−] = Ks in which Ks is the ion
product of the solvent. It is therefore unnecessary to specify both Ka and Kb, and
it has become common practice to characterize an acid–base pair by Ka only,
which may be termed the acidity constant of A–B in the solvent SH. If the value
of Kb is required it is readily obtained from Ka and Ks. Since readily accessible
values of Ka are always much less than unity, it is often convenient to introduce a
quantity pKa, sometimes called the acidity exponent, and defined by the relation
pKa = −log10Ka. Values of pKa are generally of a more convenient magnitude.

The above expressions for the various equilibrium constants depend only on the
concentrations of the species concerned, which are tacitly assumed to exist in
solution independently of one another. This is not always the case, and in exact
treatments of these equilibria two modifications are frequently necessary. In the
first place, some or all of the reacting species are ions and, because of the
electrical forces between them, the law expressing their concentrations at
equilibrium is not always valid. Corrections may be applied by multiplying the
concentrations by certain factors called activity coefficients, the values of which
can be calculated theoretically or derived from other measurements.
Furthermore, ions of opposite charge may attract one another so strongly that
they no longer exist independently but are partly present as ion pairs, thus

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 altering the forms of the equilibrium equations. For many purposes, however, the
simple equations given here are adequate, especially with regard to reactions in
aqueous solutions.

Aqueous solutions
Since aqueous solutions are of particular importance in the laboratory and in the
physiology of animals and plants, it is appropriate to consider them separately.
The ion product of water, Kw = [H3O+] [OH−], has the value 1.0 × 10−14
mole2litre−2 at 25 °C, but it is strongly temperature-dependent, becoming 1.0 ×
10−15 at 0 °C and 7 × 10−13 at 100 °C. In principle the value of Kw can be
determined by measuring the electrical conductance of very pure water, in which
[H3O+] = [OH−] = 10−7 at 25 °C, but in practice it is derived from other
measurements—for example, measurements of the degree of hydrolysis of salts.

For an uncharged acid, in this example acetic, the dissociation constant is given
by the following expression:

For acetic acid, Ka has the value 1.76 × 10−5 at 25 °C. The dissociation constant
may be expressed in terms of the degree of dissociation of the acid. This quantity,
represented by the Greek letter alpha, α, is equal to the fraction of the acid that
appears in dissociated form—in this case as the ions CH3CO2− and H3O+. If the
initial concentration of acid is designated by c, then the concentrations of the ions
are each equal to αc, or [H3O+] = [CH3CO2−] = αc, and the concentration of
undissociated acid is equal to c(1 − α), or [CH3CO2H] = c(1 − α).

Substituting these expressions into the equation giving the value of the
dissociation constant gives

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 .

From this equation it can be inferred that the degree of dissociation (α) increases
with decreasing concentration (c). For small degrees of dissociation (α < < 1), the
equation becomes

whereas, at sufficiently low concentrations (c < < 1), α tends to unity (α → 1).

Discussions exactly analogous to this apply to a number of other acid–base

equilibria—for example, (1) the dissociation of ammonia in water, (2) the
hydrolysis of ammonium salts, and (3) the hydrolysis of an acetate.

For reaction (1) α is the degree of dissociation of ammonia, and the dissociation
constant is Kb, the basic dissociation constant. In reaction (2), the hydrolysis of
an ammonium salt (for example, ammonium chloride), α would be termed the
degree of hydrolysis and K the hydrolysis constant. In terms of the general
definition of acids and bases, however, K could equally be called the acidity
constant for the acid–base pair NH4+–NH3, and this is a more rational way of
describing the process. Finally, reaction (3) represents the hydrolysis of an
acetate (for example, sodium acetate); the resulting equilibrium constant is
termed the hydrolysis constant and can be seen to equal Kw/Ka, where Kw is the
ion product of water and Ka the acidity constant for the acid–base pair
CH3CO2H–CH3CO2− (i.e., the dissociation constant of acetic acid). The

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 investigation of equilibria such as this is, in fact, one of the methods for
determining the value of Kw (see above).

The equilibria considered so far arise when one component of an acid–base pair
is dissolved in water—if necessary, along with an ion, such as Na+ or Cl−, having
negligible acid–base properties. The direct consequence of this is that the two
new species produced (for example, those on the right-hand sides of the
equations [1–3] above) have equal concentrations (αc), and hence the previously

given equation is applicable.

A solution of a more generally useful type can be obtained by deliberately

varying the proportions of acid and base present; such a solution is called a
buffered solution or, somewhat more colloquially, a buffer. A buffered solution
containing various concentrations of acetic acid and acetate ion, for example, can
be prepared by mixing solutions of acetic acid and sodium acetate, by partially
neutralizing a solution of acetic acid with sodium hydroxide, or by adding less
than one equivalent of a strong acid to a solution of sodium acetate. Similarly, a
buffer based on the pair NH4+–NH3 can be prepared by mixing solutions of
ammonia and an ammonium salt, by partially neutralizing a solution of ammonia
with a strong acid, or by adding less than one equivalent of sodium hydroxide to
a solution of an ammonium salt. The hydrogen ion concentration in a buffer
solution is, of course, still given by the usual equation, which is conveniently

written as

Since hydrogen ion concentrations are usually less than unity and cover an
extremely wide range, it is often convenient to use instead the negative logarithm
of the actual concentration, a figure that varies usually only in the range 1–13.
This figure is termed the pH, and its definition is expressed by the equation pH =
− log10[H3O+]. For example, in pure water [H3O+] = 1 × 10−7, with the result
that the pH = 7.0. The same term can be applied to alkaline solutions; thus, in 0.1

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 molar sodium hydroxide [OH−] = 0.1, [H3O+] = Kw/[OH−] = 1 × 10−14/0.1 =
10−13, and pH = 13.0.

Applying the pH concept to buffered solutions gives the following equation:

known as the buffer ratio, can be calculated from the way in

which the solution is prepared. According to this equation, the pH of the buffered
solution depends only on the pKa of the acid and on the buffer ratio. Most
particularly it does not depend on the actual concentrations of A and B.
Therefore, the pH of a buffered solution is little affected by dilution of the
solution. It is also insensitive to the addition of acid or alkali, provided that the
amounts added are much smaller than both [A] and [B]. This so-called buffering
action will be impaired if either [A] or [B] becomes too small; hence, buffer
ratios must not deviate too far from unity, and the effective buffering range of a
given acid–base system is roughly from pH = pKa + 1 to pH = pKa − 1,
corresponding to buffer ratios from 0.1 to 10.

Figure 1 shows the relation between pH and

composition for a number of commonly
used buffer systems. Effective buffer action
is confined to the central, steep portion of
each curve, where the pH is least sensitive
to the composition. Figure 1 shows that an
relation between pH and acid bearing several acidic hydrogens, such
composition as phosphoric acid, can be used to prepare
Figure 1: Relation between pH and buffer solutions in several different pH
composition for a number of
commonly used buffer systems.
ranges. Buffer action plays an important
part in controlling the pH of many
biological fluids; for example, the pH of the blood is controlled at about 7.4 by
the carbonic acid–bicarbonate system shown in Figure 1. Buffers are widely used
to control the pH in chemical or biological experiments. For the latter, the system

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 H2PO4−–HPO42− is particularly useful, being effective in the physiological pH
range, 6–8.

The same principles can be applied for the quantitative treatment of systems
containing larger numbers of acid–base pairs; for example, in an aqueous
solution of ammonium acetate, the following acid–base pairs must be considered:
NH4+–NH3, CH3CO2H–CH3CO2−, H3O–H2O, and H2O–OH−. The situation is
much more complicated in many solutions that are important in industry or in
nature, but it is always possible to make a complete prediction of the state of the
system in terms of the acidity constants Ka of each acid–base pair (provided, of
course, that reactions other than proton transfers do not interfere).

Nonaqueous solvents
Although acid–base properties have been investigated most thoroughly in
aqueous solutions, partly because of their practical importance, water is in many
respects an abnormal solvent. In particular, it has a higher dielectric constant (a
measure of the ability of the medium to reduce the force between two electric
charges) than most other liquids, and it is able itself to act either as an acid or as a
base. The behaviour of acids and bases in several other solvents will be described
briefly here.

The effect of the solvent on the dissociation of acids or bases depends largely
upon the basic or acidic properties of the solvent, respectively. Since many acid–
base reactions involve an increase or decrease in the number of ions, they are
also influenced by the dielectric constant of the solvent, for a higher dielectric
constant favours the formation of ions. Finally, the specific solvation (or close
association with the solvent) of particular ions (excluding the solvation of the
proton to give SH2+, which is already included in the basicity of the solvent) may
be important. It is usually not easy to separate these three effects and, in
particular, the effects of dielectric constant and solvation merge into one another.
These points are illustrated with examples of several of the more important

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 solvents. In this discussion the solvents are classified as amphoteric (both acidic
and basic), acidic (in which the acidic properties are much more prominent than
the basic), basic (in which the reverse is true), and aprotic (in which both acidic
and basic properties are almost entirely absent). Finally, concentrated aqueous
acids are mentioned as an example—a particularly important one—of mixed
solvents.

Amphoteric solvents
The most important nonaqueous solvents of this class are the lower alcohols
methanol and ethanol. They resemble water in their acid–base properties but,
because of their lower dielectric constants, facilitate processes producing ions to
a much smaller extent. In particular, the ion products of these solvents are much
smaller (Ks = 10−17 for CH3OH and 10−19 for C2H5OH, compared with 10−14
for water), and the dissociation constants of molecular acids and bases are
uniformly lower than in water by four to five powers of 10. Nitric acid, for
example, which is almost completely dissociated in water (Ka about 20), has Ka
= 2.5 × 10−4 in methanol. On the other hand, the equilibrium constants of
processes such as NH4+ + ROH ⇄ NH3 + ROH2+ and CH3CO2− + ROH ⇄
CH3CO2H + RO− are similar in all three solvents, since they do not involve any
change in the number of ions.

Acidic solvents
The most important strongly acidic solvent is sulfuric acid, which is able to
protonate a wide variety of compounds containing oxygen or nitrogen. Thus,
water, alcohols, ethers, ketones, nitro compounds, and sulfones all act as bases in
sulfuric acid. This solvent must also possess some basic properties, because its
ionic product is high ([H3SO4+] [HSO4−] = 1.7 × 10−4), but the basicity of the
solvent is obscured normally by its very high acidity. For example, carboxylic
acids behave as strong bases in sulfuric acid, reacting almost completely

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 according to the equation RCO2H + H2SO4 → RCO2H2+ + HSO4−. Many
substances undergo reactions in sulfuric acid that are more complicated than
simple proton transfers, often yielding species important because of their
chemical reactivity. Thus, some alcohols produce carbonium ions in sulfuric
acid; with triphenylcarbinol, for example, the reaction is (C6H5)3COH +
2H2SO4 → (C6H5)3 C+ + H3O+ + 2HSO4−. Nitric acid gives the nitronium ion,
NO2+, according to the equation HNO3 + 2H2SO4 → NO2+ + H3O+ + 2HSO4−.
This ion frequently is the active agent in the nitration of organic compounds.
Hydrogen fluoride has solvent properties resembling those of sulfuric acid but is
less acidic and has negligible basic properties. Acetic acid is another acidic
solvent that has been extensively studied. Because of its low dielectric constant,
ions exist in it largely in the form of ion pairs, and more complex associates are
frequently formed. For this reason a quantitative interpretation of acid–base
equilibria in acetic acid is often difficult, but some general conclusions can be
drawn. In particular, it can be seen that all substances more basic in water
solution than aniline react completely with acetic acid according to the equation
B + CH3CO2H → BH+ + CH3CO2−. All such bases therefore give solutions
with indistinguishable acid–base properties; this is often referred to as a levelling
effect of the solvent. The converse is true for acids; for example, the strong
mineral acids, nitric, hydrochloric, sulfuric, hydrobromic, and perchloric (HNO3,
HCl, H2SO4, HBr, and HClO4) are “levelled” in aqueous solution by complete
conversion to the hydronium ion, but in acetic acid they are differentiated as
weak acids with strengths in the approximate ratio 1:9:30:160:400.

Basic solvents
The only basic solvent that has been investigated in any detail is liquid ammonia,
which has the very low ion product [NH4+] [NH2−] = 10−33. As might be
expected, this solvent has a marked levelling effect upon acids; thus, for
example, acetic, benzoic, nitric, and hydrochloric acids all give solutions with

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 identical acidic properties, owing to the ion NH4+, although, of course, in water
they behave very differently.

Aprotic solvents
Strictly aprotic solvents include the hydrocarbons and their halogen derivatives,
which undergo no reaction with added acids or bases. Acid–base equilibrium in
these solvents can be investigated only when a second acid–base system is
added; the usual reaction A1 + B2 ⇄ B1 + A2 then takes place. Most such
investigations have employed an indicator as one of the reacting systems, but the
results are often difficult to interpret because of association of both ions and
molecules in these media of low dielectric constant.

The term aprotic has been extended recently to include solvents that are unable
to lose a proton, although they may have weakly basic properties. Some of these
aprotic solvents have high dielectric constants (for example, N, N-
dimethylformamide, dimethyl sulfoxide, and nitrobenzene) and are good solvents
for a variety of substances. They have a powerful differentiating effect on the
properties of acids and bases. In particular, basic anions are poorly solvated in
these solvents and thus behave as very strong bases; for example, it has been
estimated that sodium methoxide dissolved in dimethyl sulfoxide gives a solution
109 times as basic as in methanol.

Concentrated aqueous acids

Dilute solutions of strong acids—for example, hydrochloric, sulfuric, and
perchloric (HCl, H2SO4, HClO4)—in water behave essentially as solutions of
the ion H3O+, and their acidity increases in proportion to their concentration. At
concentrations greater than about one molar (that is, one mole of acid per litre of
solution), however, the acidity, as measured by action on indicators or by
catalytic ability, increases much more rapidly than the concentration. For
example, a 10 molar solution of any strong acid is about 1,000 times as acidic as

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 a 1 molar solution. This behaviour is undoubtedly largely due to the depletion of
water with increasing concentration of acid; the hydronium ion, H3O+, is known
to have a strong tendency to further hydration, probably mainly to the ion H3O+
(H2O)3 (that is, H9O4+), and a decrease in water content increases the proton-
donating power of the solution. The acidity of these concentrated solutions is
commonly measured by the acidity function, H0, a quantity measured by the
effect of the solvent on a basic indicator I. It is defined by H0 + pKIH+ − log10
[IH+]/[I] and becomes equal to the pH in dilute solution. The acidity function H0
frequently is found to be independent of the nature of the indicator and to give an
approximate measure of the catalytic power of the acid solution. Mixtures of
sulfuric acid and water ranging from 10 to 100 percent sulfuric acid have H0
values between −0.3 and −11.1, which corresponds to an acidity range of nearly
11 powers of 10.

Lewis acids
Much less information is available about Lewis acid–base equilibria than about
ordinary acid–base equilibria, but it is clear that the situation is less simple for
the former than for the latter. When a given Lewis acid reacts with a series of
similarly constituted bases the equilibrium constants often vary in parallel with
the conventional basic strengths. This is the case when a zinc halide, ZnX2, for
example, reacts with a series of amines. In general, however, it is not possible to
arrange Lewis acids and bases in a unique order that will predict the extent to
which a given pair will react. Thus, although the hydroxide ion (OH−) is always
a much stronger base than ammonia (NH3) in reactions with proton acids, in
reactions with the Lewis acid Ag+, the complex Ag(NH3)2+ is fairly stable,
whereas AgOH is completely dissociated. Similarly, for some metal cations
complex formation increases in the order fluoride < chloride < bromide < iodide,
whereas for other metal cations the order is the reverse of this.

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 This kind of behaviour has led to a classification of Lewis acids and bases into
“hard” and “soft” categories; as a rule, hard acids react preferentially with hard
bases and, similarly, soft acids react with soft bases. The terms hard and soft are
chosen to suggest that the atomic structures associated with hard acids and bases
are rigid and impenetrable, whereas those associated with soft acids and bases
are more readily deformable. Hard acids include the proton; sodium, calcium,
and aluminum ions; and carbonium ions. The soft acids include cuprous, silver,
mercurous, and the halogen cations. Typical soft bases are iodide, thiocyanate,
sulfide, and triphenylphosphine; whereas hard bases include hydroxide, fluoride,
and many oxyanions. The dividing line between the hard and soft categories is
not a sharp one, and its theoretical interpretation is obscure. Nevertheless, a
surprising amount of factual information can be coordinated on the basis of
preferential reactions of hard acids with hard bases and soft acids with soft bases.

The effect of molecular structure

Regularities and trends in the properties of the elements are best understood in
terms of the periodic table, an orderly pattern seen when the elements are
arranged in order of increasing atomic number. Comparing the hydrides of the
various elements in the table reveals appreciable acidity only among those of the
elements on the right-hand side of the table, especially the halogen elements—
fluorine, chlorine, bromine, and iodine. This generalization is borne out when the
elements across the first period of the table are examined in order; as the right-
hand side of the table is approached, the elements encountered are carbon,
nitrogen, oxygen, and fluorine. The hydrides of these elements show increasing
acidity. Methane, CH4, a hydride of carbon, has no detectable acidic properties,
and the pKa decreases sharply in the series ammonia (NH3), 35; water (H2O), 16;
and hydrogen fluoride (HF), 4. In any given group of the periodic table, the
acidity of the hydrides increases as the group is descended. For example, the two
groups at the right-hand side of the table include, respectively and in descending
order, the elements oxygen, sulfur, selenium, and tellurium; and fluorine,

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 chlorine, bromine, and iodine. The pKa’s of the hydrides of the first group are as
follows: water (H2O), 16; hydrogen sulfide (H2S), 7; hydrogen selenide (H2Se),
4; and hydrogen telluride (H2Te), 3. Similarly, hydrogen fluoride (HF) is a weak
acid, whereas hydrogen chloride (HCl), hydrogen bromide (HBr), and hydrogen
iodide (HI) are all completely dissociated (are strong acids) in aqueous solution.
These trends are due to variations in bond strength, electronegativity (attractive
power of the atomic nucleus for electrons), and ionic solvation energy, of which
the first is the most important. When a hydride is able to lose two or more
protons, the loss of the second is always more difficult because of the increased
negative charge on the base—e.g., H2S − HS− (pK 7), HS− − S2− (pK 15);
similarly, NH4+ − NH3 (pK 9.5), NH3 − NH2− (pK 35).

A simple rule applies to the strengths of the oxyacids, which can be given the
general formula XOn(OH)m, in which X is any nonmetal. In these compounds,
the pK decreases with increasing n but does not depend significantly upon m.
When n = 0 (e.g., ClOH, Si(OH)4), pKa is between 8 and 11; when n = 1 (e.g.,
HNO2, H2SO3) gives pKa 2–4; whereas with n = 2 or 3 (e.g., H2SO4, HClO4)
the acids are completely dissociated in water (pKa < 0). These regularities are
probably attributable to the sharing of the negative charge of the anion between n
+ 1 equivalent oxygen atoms; the more extensive the charge spread, the lower is
the energy of the anion and hence the stronger the acid.

The most important groups of organic acids are the alcohols (including the
phenols) and the carboxylic acids. The simple alcohols are very weak acids (pK
16–19); the phenols are considerably stronger (pK ∼ 10); and the carboxylic acids
stronger still (pK ∼ 5). The strength of the carboxylic acids is due to the sharing
of the negative charge between two equivalent oxygen atoms in the ion RCO2−.
The most important organic bases are the amines, RNH2, R2NH, or R3N. Most
of these are stronger bases than ammonia; i.e., their cations are weaker acids than
the ammonium ion.

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 The effect of substituents on the acid–base properties of organic molecules has
been very extensively studied and is one of the main methods of investigating the
nature of the electron displacements produced by substitution in these molecules.
The simplest classification is into electron-attracting substituents (halogens,
carbonyl, nitro, and positively charged groups) and electron-repelling groups
(alkyl groups, negatively charged groups). The electron-attracting groups make
acids stronger and bases weaker, whereas electron-repelling groups have the
opposite effects. There are, however, often more specific electronic effects,
especially in aromatic and unsaturated compounds, for which special
explanations are needed.

Dissociation constants in aqueous solution

The classical method for determining the dissociation constant of an acid or a
base is to measure the electrical conductivity of solutions of varying
concentrations. From these the degree of dissociation (α; see above) can be

determined and Ka calculated from the equation

This method is unsuitable for acids with pK less than 2 because α is then close to
unity and the value 1 − α is therefore subject to error. It also is unsuitable for
acids of pK > 7 because impurities in the solvent may affect the conductivity or
displace the dissociation equilibrium.

It is often preferable to use a more specific method for determining the

concentration of one of the species in the scheme A + H2O ⇄ B + H3O+. For
example, a hydrogen electrode (or more commonly a glass electrode, which
responds in the same way) together with a reference electrode, commonly the
calomel electrode, serves to measure the actual hydrogen ion concentration, or
the pH, of the solution. If E is the electromotive force (in volts) observed by the
electrode, the equation giving the pH is as follows:

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 In this equation, the value of E0 depends on the nature of the reference electrode
and is usually obtained by calibration with a solution of known pH.
Measurements can be made on aqueous solutions of the acid, in which case [B] =
[H3O+], but it is better to use a series of buffer solutions with known ratios
[A]/[B], since these are less sensitive to the presence of impurities. Such a series
is obtained by successive additions of alkali to a solution of the acid (or of a
strong acid to a solution of the base) and the procedure is then often termed a pH
titration.

If A and B have different optical properties—for example, if they differ in colour

or in the absorption of ultraviolet light—this property can be used to measure the
ratio [A]/[B], commonly by using an instrument called a spectrophotometer.
Since [H3O+] must also be known, the commonest procedure is to measure
[A]/[B] in a solution made by adding a small quantity of A or B to a standard
buffer solution. If A and B do not have convenient optical properties—as is
commonly the case—an indicator, that is, an acid–base system that does show a
difference in colour in changing from A to B, is used. If a small quantity of
indicator AI–BI, with acidity constant KI, is added to a buffer solution A–B, it is

easily shown that the following relation holds: in which [AI]/[BI]

is measured spectrophotometrically, and all the other quantities on the right-hand
side of the equation are known.

If accurate values of K are required, it is necessary in all the above methods to

take into account the effect of interionic forces upon the equation and the
quantities measured. This factor can induce a considerable degree of complexity
into the problem.

Selected values of acidity constants

The table contains acidity constants for selected substances. These are listed as
acids or bases according to the nature of the uncharged species, but in each case

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 the value given is pKa for the acid form (pKa and pKb for a conjugate acid–base
pair being related by the equation for aqueous solutions at
25 °C). For instances in which several values of pKa are given, these relate to
successive dissociations; e.g., for phosphoric acid, they correspond to
dissociations of H3PO4, H2PO4−, and HPO42−. All values given refer to aqueous
solutions at or near 25 °C; parentheses indicate values that have been estimated
indirectly or are uncertain for other reasons.

pKa's of representative acids and bases

Inorganic acids
boric acid 9.1 (20 °C)
hypochlorous acid 7.53 (18 °C)
hydrogen sulfide 7.0, 11.9 (18 °C)
carbonic acid 6.4, 10.3
phosphoric acid 2.1, 7.2, 12.8
sulfurous acid 1.8, 6.9 (18 °C)
nitric acid −1.6
sulfuric acid (−3), 1.9
hydrogen chloride (−7)
perchloric acid (−8)
Inorganic bases
ammonia 9.25
hydrazine −0.9, 8.23 (20 °C)
hydroxylamine 6.03 (20 °C)
Alcohols and phenols
methanol 15.5
trifluoroethanol 12.37
phenol 9.89
o-nitrophenol 7.17
m-nitrophenol 8.28

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 p-nitrophenol 7.15
o-chlorophenol 8.49
m-chlorophenol 8.85
p-chlorophenol 9.18
picric acid 0.38
Carboxylic acids
formic 3.75 (20 °C)
acetic 4.75
chloroacetic 2.85
dichloroacetic 1.48
trichloroacetic 0.70
oxalic 1.23, 4.19
malonic 2.83, 5.69
benzoic 4.19
Nitrogen bases
methylamine 10.66
dimethylamine 10.73
trimethylamine 9.81
piperidine 11.12
aniline 4.63
pyridine 5.25
quinoline 4.90 (20 °C)
pyrrole −0.27
Ronald Percy Bell

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 Citation Information
Article Title: acid–base reaction
Website Name: Encyclopaedia Britannica
Publisher: Encyclopaedia Britannica, Inc.
Date Published: 12 November 2020
URL: https://www.britannica.comhttps://www.britannica.com/science/acid-base-reaction
Access Date: February 14, 2024

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