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Fundamental Concepts of Acid-base Fundamental concepts of acid-base

equilibria Chemistry
Defining acids and bases
Key terms and concepts
Brønsted, and Lewis acids and bases
Strength of acids and bases
Dissociation of weak monoprotic acids and bases
Autoionization of water and pH, pOH, pKa, pKb
Percent ionization, Henderson-Hasselbach equation
Buffer solutions and hydrolysis of salts

Concept of the conjugate acid-base
The conjugate base of a Brønsted acid is the species
that remains when one proton has been removed from
the acid. Conversely, a conjugate acid results from the
addition of a proton to a Brønsted base.
Conjugate acid-base pairs have the following
properties:
If an acid is strong, its conjugate base has no
measurable strength.
H3O+ is the strongest acid that can exist in aqueous
solution. Acids stronger than H3O+ react with water
to produce H3O+ and their conjugate bases.

Acids weaker than H3O+ react with water to a much

smaller extent, producing H3O+ and their conjugate
bases.

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The OH- ion is the strongest base that can exist in
aqueous solution. Bases stronger than OH- react with
water to produce OH- and their conjugate acids.
For any conjugate acid-base pair it is always true that
Thus, the stronger the acid (the larger Ka), the weaker
its conjugate base (the smaller Kb), and vice versa.
Those that are weak electrolytes (partly ionized) are
weak acids and weak bases.
At equilibrium, aqueous solutions of weak acids contain
a mixture of non-ionized acid molecules, H3O+ ions,
and the conjugate base.
At equilibrium, aqueous solutions of weak bases
contain a mixture of non-ionized base molecules, OH-
ions, and the conjugate acid.
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The strength of acids and bases
Acids and bases that are strong electrolytes
(completely ionized in solution) are strong acids and
strong bases.
At equilibrium, solutions of strong acids and bases will
not contain any non-ionized acid molecules.
Weak Acids and Acid Ionization Constants
Consider a weak monoprotic acid, HA. Its ionization in
water is represented by
where Ka, the acid ionization constant, is the equilibrium
constant for the ionization of an acid.
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At a given temperature, the strength of the acid HA is
measured quantitatively by the magnitude of Ka. The
larger Ka, the stronger the acid.
Weak Bases and Base Ionization Constants
Consider a weak base, B. Its ionization in water is
represented by
where Kb, the base ionization constant, is the equilibrium
constant for the ionization of a base.
The equilibrium constant for the autoionization of water,
according to the above Equation, is
OR
where Kw is called the ion-product constant.
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At a given temperature, the strength of the base B is
measured quantitatively by the magnitude of Kb. The
larger Kb, the stronger the base.
Acid-Base Properties of Water
Water is a very weak electrolyte and therefore a poor
conductor of electricity, but it does undergo ionization
to a small extent:
OR
This reaction is sometimes called the autoionization of
water.
Whether we have pure water or an aqueous solution of
dissolved species, the following relation always holds at
25ºC:
Whenever [H+] = [OH-] the aqueous solution is said to
be neutral. In an acidic solution, there is an excess of
H+ ions and [H+] > [OH-]. In a basic solution, there is
an excess of hydroxide ions, so [H+] < [OH-].
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pH—A Measure of Acidity From the definitions of pH and pOH we obtain

The pH of a solution is defined as the negative
logarithm of the hydrogen ion concentration (in mol/L):

A pOH scale analogous to the pH scale can be devised

using the negative logarithm of the hydroxide ion
concentration of a solution. Thus, we define pOH as

The pH and Poh of a solution is a dimensionless

quantity.

Calculating the pH of Weak Acids and Weak bases

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Percent Dissociation
It is often useful to specify the amount of weak acid or
weak base that has dissociated in achieving
equilibrium in an aqueous solution. It is another
measure of the strength of an acid, which is defined as

In general, for a given weak acid, the percent

dissociation increases as the acid becomes more
dilute.

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Buffered Solutions Thus, buffers are often prepared by mixing a weak

It is a solution that has the ability to resist changes in acid or a weak base with a salt of that acid or base.
pH upon the addition of small amounts of either acid or A buffered solution may contain a weak acid and its
base. salt (for example, HF and NaF) or a weak base and its
Composition and action of buffered solutions salt (for example, NH3 and NH4Cl). By choosing the
A buffer resists changes in pH because it contains both appropriate components, a solution can be buffered at
an acid to neutralize added OH- ions and a base to virtually any pH.
neutralize added ions. The acid and base that make up
the buffer, however, must not consume each other
through a neutralization reaction. These requirements
are fulfilled by a weak acid–base conjugate pair, such
as CH3COOH–CH3COO- or NH4+ –NH3

Calculating the pH of a Buffer

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Buffering action: How Does It Work?
What if some acid (H+) is added?
If H+ ions are added, they react with the base
component of the buffer:
This reaction causes [HA] to increase and [A-] to
decrease. But, as long as some A- remains, the system
is still a mixture of HA and A-. Therefore, the general
equation,
still applies. Thus, [H+] is still ≈ Ka
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What if some base (OH-) is added instead?
The added base (OH-) will neutralize some of the acid
HA and produce more of the conjugate base, A-
This reaction causes [HA] to decrease and [A-] to
increase. But, as long as some HA remains, the system
is still a mixture of HA and A-, and it is still a buffer
solution.
The shift in ionic equilibrium that occurs when a solute
containing an ion that takes part in the equilibrium is
added to a solution at equilibrium is known as the
common-ion effect.
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Preparing a buffer solution with a specific pH Taking the negative logarithm of both sides of the
Let’s consider one composed of a weak acid HX and equation, we have
one of its salts MX. The acid-dissociation equilibrium in
this buffered solution involves both the acid and its
conjugate base:

The above equation is known as the Henderson– The pH of a Buffered Solution

Hasselbalch equation.

The pKa of the weak acid to be used in the buffer

should be as close as possible to the desired pH.

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SAMPLE PROBLEM
Try these problems at home
3. Lactic acid (CH3CH (OH) COOH) has a pKa of 3.08.
What is the approximate degree of dissociation of a 0.35M
solution of lactic acid?
Salts that produce neutral solutions
Salts that consist of the cations of strong bases and the
anions of strong acids have no effect on [H+] when
dissolved in water. This means that aqueous solutions
of salts such as KCl, NaCl, NaNO3, and KNO3 are
neutral.
Salts that produce basic solutions
In general, for any salt whose cation has neutral
properties (such as Na+or K+) and whose anion is the
conjugate base of a weak acid, the aqueous solution
will be basic. This means that aqueous solutions of
salts such as NaClO, RbF, BaSO3 are basic.
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Acid-base properties of salt solutions
A salt is an ionic compound formed by the reaction
between an acid and a base.
Salts are strong electrolytes that completely dissociate
in water and in some cases react with water.
The term salt hydrolysis describes the reaction of an
anion or a cation of a salt, or both, with water.
Salt hydrolysis usually affects the pH of a solution.
Thus, the pH of an aqueous salt solution can be
predicted qualitatively by considering the salt’s cations
and anions.
Salts that produce acidic solutions
In general, salts in which the anion is not a base and
the cation is the conjugate acid of a weak base
produce acidic solutions. This means that aqueous
solutions of salts such as NH4NO3, AlCl3, Fe(NO3)3 are
acidic.
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Solving salt hydrolysis problems

Follow the same procedure we used for weak acids
and weak bases.

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Salts in which both the cation and the anion Equal Ka and Kb values mean a neutral solution.
hydrolyze The acid–base properties of aqueous solutions of
If the salt contains an anion and a cation both capable various salts are summarized in Table 14.6
of reacting with water, both hydroxide ions and
hydronium ions are produced. Examples: NH4ClO,
Al(CH3COO)3, CrF3.
To predict whether the solution will be basic, acidic, or
neutral, it depends on the Ka value for the acidic ion
and the Kb value for the basic ion.
If the Ka value for the acidic ion is larger than the Kb
value for the basic ion, the solution will be acidic.
If the Kb value is larger than the Ka value, the
solution will be basic.

THANK YOU

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