Definitions of Acids and Bases, and the Role of Water

Nahkleh Group
Robinson Group
Weaver Group
Bodner Group

Acids and Bases

Definitions of Acids and Bases and the Role of Water

Acid-Base Pairs, Strength of Acids and Bases, and pH

Factors that Control the Relative Strengths of Acids and Bases

Brønsted Acids and Bases

Transition Metal Ions as Brøntsed Acids

The Lewis Definitions of Acids and Bases

Definitions of Acids and Bases

and the Role of Water

Properties of Acids and The Arrhenius The Role of H+ and

Bases According to Definition of Acids OH- Ions In the
Boyle and Bases Chemistry of Aqueous
Solutions

To What Extent Does The Operational Typical Acids and

Water Dissociate to Definition of Acids Bases
Form Ions? and Bases

Why are Metal The Brnsted The Role of Water in

Hydroxides Bases and Definition of Acids the Brnsted Theory
Nonmetal Hydroxides and Bases
Acids?
 Properties of Acids and Bases According to Boyle

In 1661 Robert Boyle summarized the properties of acids as follows.

1. Acids have a sour taste.

2. Acids are corrosive.

3. Acids change the color of certain vegetable dyes, such as litmus, from
blue to red.

4. Acids lose their acidity when they are combined with alkalies.

The name "acid" comes from the Latin acidus, which means "sour," and
refers to the sharp odor and sour taste of many acids.

Examples: Vinegar tastes sour because it is a dilute solution of acetic

acid in water. Lemon juice tastes sour because it contains citric acid.
Milk turns sour when it spoils because lactic acid is formed, and the
unpleasant, sour odor of rotten meat or butter can be attributed to
compounds such as butyric acid that form when fat spoils.

In 1661 Boyle summarized the properties of alkalies as follows.

● Alkalies feel slippery.

● Alkalies change the color of litmus from red to blue.
● Alkalies become less alkaline when they are
combined with acids.

In essence, Boyle defined alkalies as substances that consume, or

neutralize, acids. Acids lose their characteristic sour taste and ability to
dissolve metals when they are mixed with alkalies. Alkalies even reverse
the change in color that occurs when litmus comes in contact with an
acid. Eventually alkalies became known as bases because they serve as
the "base" for making certain salts.

The Arrhenius Definition of Acids and Bases

In 1884 Svante Arrhenius suggested that salts such as NaCl dissociate

when they dissolve in water to give particles he called ions.

H2O

NaCl(s) Na+(aq) + Cl-(aq)

 Three years later Arrhenius extended this theory by suggesting that
acids are neutral compounds that ionize when they dissolve in water to
give H+ ions and a corresponding negative ion. According to his theory,
hydrogen chloride is an acid because it ionizes when it dissolves in water
to give hydrogen (H+) and chloride (Cl-) ions as shown in the figure
below.

H2O

HCl(g) H+(aq) + Cl-(aq)

Arrhenius argued that bases are neutral compounds that either

dissociate or ionize in water to give OH- ions and a positive ion. NaOH is
an Arrhenius base because it dissociates in water to give the hydroxide
(OH-) and sodium (Na+) ions.

H2O

NaOH(s) Na+(aq) + OH-(aq)

An Arrhenius acid is therefore any substance that ionizes when it

dissolves in water to give the H+, or hydrogen, ion.

An Arrhenius base is any substance that gives the OH-, or hydroxide,

ion when it dissolves in water.

Arrhenius acids include compounds such as HCl, HCN, and H 2SO4 that
ionize in water to give the H+ ion. Arrhenius bases include ionic
compounds that contain the OH- ion, such as NaOH, KOH, and Ca(OH)2.

This theory explains why acids have similar properties: The

characteristic properties of acids result from the presence of the H + ion
generated when an acid dissolves in water. It also explains why acids
neutralize bases and vice versa. Acids provide the H + ion; bases provide
the OH- ion; and these ions combine to form water.

H+(aq) + OH-(aq) H2O(l)

The Arrhenius theory has several disadvantages.

● It can be applied only to reactions that occur in

water because it defines acids and bases in terms of
what happens when compounds dissolve in water.
● It doesn't explain why some compounds in which
hydrogen has an oxidation number of +1 (such as
HCl) dissolve in water to give acidic solutions,
whereas others (such as CH4) do not.
● Only the compounds that contain the OH- ion can be
classified as Arrhenius bases. The Arrhenius theory
can't explain why other compounds (such as Na2CO3)
have the characteristic properties of bases.

The Role of H+ and OH- Ions In the Chemistry of Aqueous

Solutions

Becuase oxygen (EN = 3.44) is much more electronegative than

hydrogen (EN = 2.20), the electrons in the H O bonds in water aren't
shared equally by the hydrogen and oxygen atoms. These electrons are
drawn toward the oxygen atom in the center of the molecule and away
from the hydrogen atoms on either end. As a result, the water molecule
is polar. The oxygen atom carries a partial negative charge ( -), and
the hydrogen atoms carry a partial positive charge ( +).

When they dissociate to form ions, water molecules therefore form a

positively charged H+ ion and a negatively charged OH- ion.

The opposite reaction can also occur H+ ions can combine with OH-
ions to form neutral water molecules.
The fact that water molecules dissociate to form H+ and OH- ions, which
can then recombine to form water molecules, is indicated by the
following equation.

To What Extent Does Water Dissociate to Form Ions?

At 25C, the density of water is 0.9971 g/cm3, or 0.9971 g/mL. The

concentration of water is therefore 55.35 molar.

The concentration of the H+ and OH- ions formed by the dissociation of

neutral H2O molecules at this temperature is only 1.0 x 10 -7 mol/L. The
ratio of the concentration of the H+ (or OH-) ion to the concentration of
the neutral H2O molecules is therefore 1.8 x 10-9.

In other words, only about 2 parts per billion (ppb) of the water
molecules dissociate into ions at room temperature. The figure below
shows a model of 20 water molecules, one of which has dissociated to
form a pair of H+ and OH- ions. If this illustration was a very-high-
resolution photograph of the structure of water, we would encounter a
pair of H+and OH- ions on the average of only once for every 25 million
such photographs.
 The Operational Definition of Acids and Bases

The fact that water dissociates to form H+ and OH- ions in a reversible
reaction is the basis for an operational definition of acids and bases that
is more powerful than the definitions proposed by Arrhenius. In an
operational sense, an acid is any substance that increases the
concentration of the H+ ion when it dissolves in water. A base is any
substance that increases the concentration of the OH - ion when it
dissolves in water.

These definitions tie the theory of acids and bases to a simple laboratory
test for acids and bases. To decide whether a compound is an acid or a
base we dissolve it in water and test the solution to see whether the H +
or OH- ion concentration has increased.

Typical Acids and Bases

The properties of acids and bases result from differences between the
chemistry of metals and nonmetals, as can be seen from the chemistry
of these classes of compounds: hydrogne, oxides, and hydroxides.

Compounds that contain hydrogen bound to a nonmetal are called

nonmetal hydrides. Because they contain hydrogen in the +1 oxidation
state, these compounds can act as a source of the H + ion in water.

Metal hydrides, on the other hand, contain hydrogen bound to a metal.

Because these compounds contain hydrogen in a -1 oxidation state,
they dissociate in water to give the H- (or hydride) ion.

The H- ion, with its pair of valence electrons, can abstract an H + ion from
a water molecule.
 Since removing H+ ions from water molecules is one way to increase the
OH- ion concentration in a solution, metal hydrides are bases.

A similar pattern can be found in the chemistry of the oxides formed by

metals and nonmetals. Nonmetal oxides dissolve in water to form acids.
CO2 dissolves in water to give carbonic acid, SO3 gives sulfuric acid, and
P4O10 reacts with water to give phosphoric acid.

Metal oxides, on the other hand, are bases. Metal oxides formally
contain the O2- ion, which reacts with water to give a pair of OH - ions.

Metal oxides therefore fit the operational definition of a base.

We see the same pattern in the chemistry of compounds that contain

the OH, or hydroxide, group. Metal hydroxides, such as LiOH, NaOH,
KOH, and Ca(OH)2, are bases.

Nonmetal hydroxides, such as hypochlorous acid (HOCl), are acids.

The table below summarizes the trends observed in these three

categories of compounds. Metal hydrides, metal oxides, and metal
hydroxides are bases. Nonmetal hydrides, nonmetal oxides, and
nonmetal hydroxides are acids.

Typical Acids and Bases

Acids Bases

Non-metal Hydrides Metal Hydrides

HF, HCl, HBr, HCN, HI, LiH, NaH,
HSCN, H2S KH, MgH2, CaH2

Non-metal Oxides Metal Oxides

CO2, SO2, SO3, Li2O, Na2O, K2O,
NO2, P4O10 MgO, CaO

Non-metal Hydroxides Metal Hydroxides

HOCl, HONO2, LiOH, NaOH, KOH,
O2S(OH)2, OP(OH)3 Ca(OH)2, Ba(OH)2

The acidic hydrogen atoms in the non-metal hydroxides in the table

above aren't bound to the nitrogen, sulfur, or phosphorus atoms. In
each of these compounds, the acidic hydrogen is attached to an oxygen
atom. These compounds are therefore all examples of oxyacids.

Skeleton structures for eight oxyacids are given in the figure below. As a
general rule, acids that contain oxygen have skeleton structures in
which the acidic hydrogens are attached to oxygen atoms.
Practice Problem 1:

Use Lewis structures to classify the following acids as either nonmetal

hydrides (XH) or nonmetal hydroxides (XOH).

(a) HCN

(b) HNO3

(c) H2C2O4

(d) CH3CO2H

Click here to check your answer to Practice Problem 1

Why are Metal Hydroxides Bases and Nonmetal Hydroxides

Acids?

To understand why nonmetal hydroxides are acids and metal hydroxides

are bases, we have to look at the electronegativities of the atoms in
these compounds. Let's start with a typical metal hydroxide: sodium
hydroxide

The difference between the electronegativities of sodium and oxygen is

very large ( EN = 2.5). As a result, the electrons in the Na O bond
are not shared equally these electrons are drawn toward the more
electronegative oxygen atom. NaOH therefore dissociates to give Na +
and OH- ions when it dissolves in water.

We get a very different pattern when we apply the same procedure to

hypochlorous acid, HOCl, a typical nonmetal hydroxide.
Here, the difference between the electronegativities of the chlorine and
oxygen atoms is small ( EN = 0.28). As a result, the electrons in the Cl
O bond are shared more or less equally by the two atoms. The O
H bond, on the other hand, is polar ( EN = 1.24) the electrons in
this bond are drawn toward the more electronegative oxygen atom.
When this molecule ionizes, the electrons in the O-H bond remain with
the oxygen atom, and OCl- and H+ ions are formed.

There is no abrupt change from metal to nonmetal across a row or down

a column of the periodic table. We should therefore expect to find
compounds that lie between the extremes of metal and nonmetal
oxides, or metal and nonmetal hydroxides. These compounds, such as
Al2O3 and Al(OH)3, are called amphoteric (literally, "either or both")
because they can act as either acids or bases. Al(OH) 3, for example,
acts as an acid when it reacts with a base.

Conversely, it acts as a base when it reacts with an acid.

The Brnsted Definition of Acids and Bases

The Brnsted, or Brnsted-Lowry, model is based on a simple assumption:

Acids donate H+ ions to another ion or molecule, which acts as a
base. The dissociation of water, for example, involves the transfer of an
H+ ion from one water molecule to another to form H 3O+ and OH- ions.
According to this model, HCl doesn't dissociate in water to form H + and
Cl+ ions. Instead, an H+ ion is transferred from HCl to a water molecule
to form H3O+ and Cl- ions, as shown in the figure below.

Because it is a proton, an H+ ion is several orders of magnitude smaller

than the smallest atom. As a result, the charge on an isolated H + ion is
distributed over such a small amount of space that this H + ion is
attracted toward any source of negative charge that exists in the
solution. Thus, the instant that an H+ ion is created in an aqueous
solution, it bonds to a water molecule. The Brnsted model, in which H +
ions are transferred from one ion or molecule to another, therefore
makes more sense than the Arrhenius theory, which assumes that H +
ions exist in aqueous solution.

Even the Brnsted model is naive. Each H+ ion that an acid donates to
water is actually bound to four neighboring water molecules, as shown
in the figure below.