3.

Acid-Base equilibrium
 Specific content

●
Acid-base models of Arrhenius, Brönsted-Lowry, and Lewis
●
Dissociation of acids, bases and salts in water.
●
Relative strength of acids and bases (Ka and Kb).
●
Conjugated acid-base pair.
●
Water dissociation (Autoionization) and the concepts of pH and pOH, pH scale
●
pH determination of acids, bases and salts in aqueous solution.
●
Buffer solutions (regulators): composition, properties, buffer capacity.
●
Acids and bases titration curves for simple and multiple equilibria
●
Buffer solutions for multiple equilibrium systems
 Specific content

●
Acid-base models of Arrhenius, Brönsted-Lowry, and Lewis
●
Dissociation of acids, bases and salts in water.
●
Relative strength of acids and bases (Ka and Kb).
●
Conjugated acid-base pair.
●
Water dissociation (Autoionization) and the concepts of pH and pOH, pH scale
●
pH determination of acids, bases and salts in aqueous solution.
●
Buffer solutions (regulators): composition, properties, buffer capacity.
●
Acids and bases titration curves for simple and multiple equilibria
●
Buffer solutions for multiple equilibrium systems
 The arrhenius theory
1680: Robert Boyle noted that acids dissolve many substances, change the colors of some
natural dyes (indicators),and lose their characteristic properties when mixed with alkalis
(bases).

1814, J. Gay-Lussac concluded that acids neutralize bases and that the two classes of
substances should be defined in terms of their reactions with each other.

1884, Svante Arrhenius (1859–1927) presented his theory of electrolytic dissociation, which
resulted in the Arrhenius theory of acid–base reactions. In his view,

An acid is a substance that contains hydrogen and produces H+ in aqueous

solution. A base is a substance that contains the OH (hydroxyl) group and
produces hydroxide ions, OH-, in aqueous solution.
 The arrhenius theory
An acid is a substance that contains hydrogen and produces H + in
aqueous solution. A base is a substance that contains the OH (hydroxyl)
group and produces hydroxide ions, OH-, in aqueous solution.

Neutralization is defined as the combination of H+ ions with OH- ions to form

H2O molecules.
 The hydronium ion (hydrated hydrogen ion)
H+ ions are hydrated in aqueous solution and exist as H+(H2O)n, in which n is
some small integer. This is due to the attraction of the H+ ions, or protons, for
the oxygen end (δ-) of water molecules.
 The Brønsted–Lowry theory
1923, J.N. Brønsted (1879–1947) and T.M. Lowry (1874–1936) independently
presented logical extensions of the Arrhenius theory. Brønsted’s contribution
was more thorough than Lowry’s, and the result is known as the Brønsted
theory or the Brønsted–Lowry theory.

An acid is defined as a proton donor (H+) and a base is defined as a proton

acceptor.

These definitions are sufficiently broad that any hydrogen-containing molecule or ion
capable of releasing a proton, H+, is an acid, whereas any molecule or ion that can accept
a proton is a base. (In the Arrhenius theory of acids and bases, only substances that
contain the OH+ group would be called bases.)
The Brønsted–Lowry theory
 The Lewis Theory for acids and bases
1932: The chemist G. N. Lewis postulated a definition for acids and bases: A Lewis
base as a substance that can donate a pair of electrons. A Lewis acid is a substance
capable of accepting a pair of electrons.

Lewis base Lewis acid

Lewis acid-base reactions include many reactions in which Brønsted-Lowry acids do not
participate
Dissociation of acids, bases and salts in water.

Dissolution when the the

solute reacts with the
solvent

Dissolution when the the

solute do not react with the
solvent
Dissociation of acids, bases and salts in water.

vs.
Dissociation of acids, bases and salts in water.
Relative strength of acids and bases (Ka and Kb)

-log(Ka)

-log(Kb)
 Specific content
●
Acid-base models of Arrhenius, Brönsted-Lowry, and Lewis
●
Dissociation of acids, bases and salts in water.
●
Relative strength of acids and bases (Ka and Kb).
●
Conjugated acid-base pair.
●
Water dissociation (Autoionization) and the concepts of pH and pOH, pH
scale
●
pH determination of acids, bases and salts in aqueous solution.
●
Buffer solutions (regulators): composition, properties, buffer capacity.
●
Acids and bases titration curves for simple and multiple equilibria
●
Buffer solutions for multiple equilibrium systems
Conjugated acid and base pairs

A strong acid
has a weak
conjugated base
and vice versa.
 The autoionization of water

Activity = 1

The formation of an H3O+ by the ionization of water is always accompanied by the

formation of an OH-. Thus, in pure water the concentration of H3O+ is always
equal to the concentration of OH-. Careful measurements show that, in pure
water at 25°C,
 The autoionization of water
Calculate the concentrations of H3O and OH- ions in a 0.050 M HNO3 solution.
 Specific content
●
Acid-base models of Arrhenius, Brönsted-Lowry, and Lewis
●
Dissociation of acids, bases and salts in water.
●
Relative strength of acids and bases (Ka and Kb).
●
Conjugated acid-base pair.
●
Water dissociation (Autoionization) and the concepts of pH and pOH, pH
scale
●
pH determination of acids, bases and salts in aqueous solution.
●
Buffer solutions (regulators): composition, properties, buffer capacity.
●
Acids and bases titration curves for simple and multiple equilibria
●
Buffer solutions for multiple equilibrium systems
 pH determination
The pH and pOH scales provide a convenient way to express the acidity and
basicity of dilute aqueous solutions. The pH and pOH of a solution are defined as
 pH determination
A convenient relationship between pH and pOH in all dilute solutions at 25°C can be easily
derived. We start with the Kw expression.

Taking the logarithm of both sides of this equation gives

Multiplying both sides of this equation by 1 gives

pH determination
pH determination
 pH determination
Calculate [H3O+], pH, [OH-], and pOH for a 0.015 M Ca(OH)2 solution.
pH determination: Calculation of Ka from Percent
Ionization
In 0.0100 M solution, acetic acid is 4.2% ionized. Calculate its ionization constant.
 pH determination: Calculation of Ka from pH
The pH of a 0.115 M solution of chloroacetic acid, ClCH2COOH, is measured to be 1.92.
Calculate Ka for this weak monoprotic acid.
 pH determination: Calculation of Concentrations
from Ka
Calculate the concentrations of the various species in 0.10 M hypochlorous acid, HOCl. For
HOCl, Ka 3.5 x10-8.
 pH determination: Percent Ionization
Calculate the percent ionization of a 0.10 M solution of acetic acid. (Ka = 1,8 x 10-5)
 pH determination: Percent Ionization and pH.
Complete the next table
 Specific content

●
Acid-base models of Arrhenius, Brönsted-Lowry, and Lewis
●
Dissociation of acids, bases and salts in water.
●
Relative strength of acids and bases (Ka and Kb).
●
Conjugated acid-base pair.
●
Water dissociation (Autoionization) and the concepts of pH and pOH, pH
scale
●
pH determination of acids, bases and salts in aqueous solution.
●
Buffer solutions (regulators): composition, properties, buffer capacity.
●
Acids and bases titration curves for simple and multiple equilibria
●
Buffer solutions for multiple equilibrium systems
 The common ion effect and buffer solutions
A buffer solution contains a conjugate acid–base pair with both the acid and base in
reasonable concentrations. The acidic component reacts with added strong bases. The
basic component reacts with added strong acids.
The operation of a buffer solution depends on the common ion effect, a special case of
LeChatelier’s Principle.

Many types of solutions exhibit this behavior. Two of the most frequently encountered
kinds are:
1. A solution of a weak acid plus a soluble ionic salt of the weak acid (e.g.,
CH3COOH/CH3COONa)
2. A solution of a weak base plus a soluble ionic salt of the weak base (e.g., NH3/NH4Cl)
 Weak Acids Plus Salts of Weak Acids
Consider a solution that contains acetic acid and sodium acetate, a soluble ionic salt of
CH3COOH.

Solutions that contain a weak acid plus a salt of the weak acid are always less acidic than
solutions that contain the same concentration of the weak acid alone.
 Weak Acids Plus Salts of Weak Acids
What is the pH of a 0.1 M CH3COOH solution? What is the pH of a 0.1 M CH3COOH
solution prepared in a 0.2 M CH3COONa solution?
 Henderson–Hasselbalch equation

Consider a solution in which the concentrations of both the weak acid and its anion (from an
added salt) are some reasonable values, such as greater than 0.050 M. Under these
conditions the concentration of the anion, [A], in the solution can be assumed to be entirely
due to the dissolved salt. With these restrictions, the preceding expression becomes.
 Henderson–Hasselbalch equation
Use the Henderson–Hasselbalch equation to calculate the pH of the buffer solution for a
mixture composed by 0.10 M inCH3COOH and 0.20 M in CH3COONa
 Weak Bases Plus Salts of Weak Bases
Let us consider the second common kind of buffer solution, containing a weak base and its
salt. A solution that contains aqueous NH3 and ammonium chloride, NH4Cl, a soluble ionic
salt of NH3.

Solutions that contain a weak base plus a salt of the weak base are always less basic than
solutions that contain the same concentration of the weak base alone.
 Weak Bases Plus Salts of Weak Bases
Calculate the concentration of OH- and the pH of a solution that is 0.20 M in aqueous NH3 and
the pH when 0.10 M in NH4Cl is added
 Henderson–Hasselbalch equation

We can derive a relationship for [OH] in a solution containing a weak base, B, plusa salt that
contains the cation, BH, of the weak base, just as we did for weak acids.

Multiplication
by -1
 Buffering action
A buffer solution is able to react with either H3O+ or OH- ions, whichever is added. Thus, a
buffer solution resists changes in pH. When we add a modest amount of a strong base or a
strong acid to a buffer solution, the pH changes very little.

If we add a strong acid such as HCl to this solution, it produces H3O+. As a result of the
added H3O+, the reaction occurs to the left, to use up most of the added H3O+ and reestablish
equilibrium.

or
 Buffering action
When a strong base, such as NaOH, is added to the CH3COOH–NaCH3COO buffer solution, it
is consumed by the acidic component, CH3COOH. This occurs in the following way.
 Buffering action
If we add 0.010 mol of solid NaOH to 1.00 liter of a buffer solution that is 0.100 M in
CH3COOH and 0.100 M inCH3COONa, how much will [H3O+] and pH change? Assume
that there is no volume change due to the addition of solid NaOH.
What is the pH change if the same quantity of NaOH is added to 0.1 M solution of
CH3COOH? What is the pH change if it is added to pure water?
 Preparation of buffer solutions
Calculate the grams necessary for preparing 300 mL of a 0.01 M buffer solution with pH
7.2 composed by NaH2PO4 and K2HPO4. (Phosphate buffer solution, PBS).

Ka1 = 7.11 x 10-3 ka2 = 6.32 x 10-8 ka3 = 4.5 x 10-13

 Specific content

●
Acid-base models of Arrhenius, Brönsted-Lowry, and Lewis
●
Dissociation of acids, bases and salts in water.
●
Relative strength of acids and bases (Ka and Kb).
●
Conjugated acid-base pair.
●
Water dissociation (Autoionization) and the concepts of pH and pOH, pH
scale
●
pH determination of acids, bases and salts in aqueous solution.
●
Buffer solutions (regulators): composition, properties, buffer capacity.
●
Acids and bases titration curves for simple and multiple equilibria
●
Buffer solutions for multiple equilibrium systems
 Titration curves.
A titration curve is a plot of pH versus the amount (usually volume) of acid or base
added. It displays graphically the change in pH as acid or base is added to a solution and
shows how pH changes near the equivalence point.
The point at which the color of an indicator changes (or a considerable changei in pH is
measured) in a titration is known as the end point. The equivalence point is the point at
which chemically equivalent amounts of acid and base have reacted.
Ideally, the end point and the equivalence point in a titration should coincide.
 Strong Acid/Base titration curves.
Consider the titration of 100.0 mL of a 0.100 M solution of HCl with a 0.100 M solution of NaOH.
NaOH and HCl react in a 1:1 ratio. We calculate the pH of the solution at several stages as NaOH
is added
1. Before any NaOH is added to the 0.100 M HCl solution:

2. After 20.0 mL of 0.100 M NaOH has been added:

 Strong Acid/Base titration curves.

2. After 20.0 mL of 0.100 M NaOH has been added:

 Strong Acid/Base titration curves.
3. After 100. mL of 0.100 M NaOH has been added (equivalence point)

The solution is neutralized. The pH is given for the autoionization of water:

[H3O+] = Kw1/2 = 1x10-7

PH = 7.0
 Strong Acid/Base titration curves.
4. After 110.0 mL of 0.100 M NaOH has been added:
Strong Acid/Base titration curves.
 Weak Acid/Base titration curves
When a weak acid is titrated with a strong base, the curve is quite different. The solution
is buffered before the equivalence point. It is basic at the equivalence point because
salts of weak acids and strong bases hydrolyze to give basic solutions. So, we can
separate the calculations on this kind of titration into four distinct types, which correspond
to fourregions of the titration curves.

1. Before any base is added, the pH depends on the weak acid alone.
2. After some base has been added, but before the equivalence point, a series of weak
acid/salt buffer solutions determines the pH.
3. At the equivalence point, hydrolysis of the anion of the weak acid determines the pH.
4. Beyond the equivalence point, excess strong base determines the pH

Consider the titration of 100.0 mL of 0.100 M CH3COOH with 0.100 M NaOH solution. (The
strong electrolyte is added to the weak electrolyte.)
 Weak Acid/Base titration curves
1. Before any base is added, the pH is 2.89 (why?)

2. As soon as some NaOH is added, but before the equivalence point, the solution is buffered
because it contains both CH3COOH and CH3COONa.

For instance, after 20.0 mL of 0.100 M NaOH solution has been added, we have
 Weak Acid/Base titration curves
3. At the equivalence point, the solution is 0.0500 M in CH3COONa
 Weak Acid/Base titration curves
4. Beyond the equivalence point, the concentration of the excess NaOH determines the pH
of the solution just as it did in the titration of a strong acid.
Weak Acid/Base titration curves