 ClassifyingSolutions of Electrolytes

Most of the solutes are

electrolytes, which form ions when
dissolved in water (or certain other
solvents) and thus produce
solutions that conduct electricity.
 Classifying Solutions of Electrolytes
In a solvent, strong electrolytes
ionize essentially completely,
whereas weak electrolytes ionize
only partially.
◦ Table 1 is a compilation of solutes
that act as strong and weak
electrolytes in water.

2-3
2-4
 Brønsted and Lowry proposed
independently a theory of acid /
base behavior that is particularly
useful in analytical chemistry.
According to the Brønsted –Lowry
theory, an acid is a proton donor
and a base is a proton acceptor.

2-5
 Conjugate base

 Conjugate acid

 Neutralization
(2-4)

(2-5)

2-7
 Some species have both acidic and
basic properties and are called
amphiprotic solutes, as illustrated in
Feature 2-4.

2-8
 A zwitterion is an ion that bears both
a positive and a negative charge.

2-9
• Amphiprotic Solvents

− Amphiprotic solvents behave as acids in

the presence of basic solutes and bases
in the presence of acidic solutes. (2-6)

(2-7)

2-10
 Autoprotolysis

2-11
 Solvents and Autoprotolysis
 The hydronium ion is the
hydrated proton formed when
water reacts with an acid. It is
usually formulated as H3O+,
although several higher
hydrates exist.

3-12
 Figure 1 shows the dissociation reaction
of a few common acids in water.
 Strong acids react with water so
completely that no undissociated solute
molecules remain. The others are weak
acids, which react incompletely with
water to give solutions that contain
significant amounts of both the parent
acid and its conjugate base.

2-13
Figure 1 Dissociation reactions and relative
strengths of some common acids and their
conjugate bases. Note that HCl and HClO4 are
completely dissociated in water. 2-14
Strong and Weak Acids and Bases

 Ina differentiating solvent,

various acids dissociate to
different degrees and thus have
different strengths. In a leveling
solvent, several acids are
completely dissociated and are
thus of the same strength.

3-15
 Equilibrium-constant expressions are
algebraic equations that describe the
concentration relationships that exist
among reactants and products at
equilibrium.
 Among other things, equilibrium-
constant expressions permit us to
calculate the error that results from
any unreacted analyte remaining when
equilibrium has been reached.
2-16
 The rate of this reaction and the extent to
which it proceeds to the right can be readily
monitored by observing the orange-red color
of the triiodide ion (the other participants in
the reaction are colorless) as it increases with
time. If, for example, we add 1 mmol of
arsenic acid H3AsO4 to 100 mL of a solution
containing 3 mmol of potassium iodide, the
red color of the triiodide ion appears almost
immediately, and within a few seconds the
intensity of the color becomes constant, which
shows that the triiodide concentration has
become constant . 2-17
 Theconcentration relationship at
chemical equilibrium (that is, the
position of equilibrium) is
independent of the route by which
the equilibrium state is achieved.

2-18
 The Le Châtelier principle states that
the position of an equilibrium always
shifts in such a direction as to relieve
a stress that is applied to the system.
 Mass action effect.
◦ The mass-action effect is a shift in
the position of an equilibrium
caused by adding one of the
reactants or products to a system.
2-19
 Chemical reactions do not cease at
equilibrium. Instead, the amounts of
reactants and products are constant
because the rates of the forward and
reverse processes are identical.
 Equilibrium-constant expressions
provide no information as to whether a
chemical reaction is fast enough to be
useful in an analytical procedure.
2-20
 (2-9)

Equilibrium (2-10)
constant

2-21
2-22
 If one (or more) of the species in
Equation 2-10 is a pure liquid, a pure
solid, or the solvent present in excess,
no term for this species appears in the
equilibrium constant expression.

 Equation 2-10
 The constant K in Equation 2-10 is a
temperature-dependent numerical
quantity called the equilibrium
constant.
3-23
• [Z]Z in Equation 2-10 is replaced with pz in
atmospheres if Z is a gas. No term for Z is
included in the equation if this species is a pure
solid, a pure liquid, or the solvent of a dilute
solution.
• Remember: Equation 2-10 is only an
approximate form of an equilibrium-constant
expression. The exact expression takes the form

3-24
 Why [H2O] Does Not Appear in
Equilibrium- Constant Expressions
for Aqueous Solutions
◦ In a dilute aqueous solution, the
molar concentration of water is

2-25
The Ion-Product Constant for Water

2-26
The percent change in water
concentration in an aqueous
solution is usually
inconsequential. Thus, K[H2O]2 is,
for all practical purposes, a
constant. That is,

2-27
ion-product constant for water

2-28
 Calculate
the hydronium and
hydroxide ion concentrations
of pure water at 25°C and
100°C.

2-29
 Because OH- and H3O+ are formed
only from the dissociation of water,
their concentrations must be equal:

Substitution into the equation gives

2-30
 At 25°C,

 At 100°C, from Table 3,

2-31
3-32
• What are Solubility-Products?

2-33
Solubility-product constant or
the solubility product
(2-15)

For Equation 2-15 to apply, it is

necessary only that some solid be
present. In the absence of
Ba(IO3)(s), Equation 2-15 is not
valid.
2-34
 Whatmass of Ba(IO3)2 (487
g/mol) can be dissolved in
500.0 mL of water at 25°C?

2-35
2-36
• Note that the molar solubility is
equal to 1 [IO ] or to [Ba2+]
3
.
2

2-37
2-38
2-39
 How Does a Common Ion Affect the
Solubility of a Precipitate?
◦ The common ion effect is a mass-action
effect predicted from the Le Châtelier
principle.
◦ The common-ion effect is responsible for
the reduction in solubility of an ionic
precipitate when a soluble compound
combining one of the ions of the
precipitate is added to the solution in
equilibrium with the precipitate. 2-40
 Calculatethe molar solubility
of Ba(IO3)2 in a solution that is
0.0200 M in Ba(NO3)2 .

2-41
 Calculate the molar solubility of
Ba(IO3)2 in a solution that is
0.0200 M in Ba(NO3)2 .

2-42
 The assumption
that does
not appear to cause serious error
2-43
 Ordinarily,we consider an
assumption of this type to be
satisfactory if the discrepancy is
less than 10%. Finally, then,

2-44
 Calculate the solubility of
Ba(IO3)2 in a solution prepared
by mixing 200 mL of 0.0100 M
Ba(NO3)2 with 100 mL of 0.100
M NaIO3 .

2-45
2-46
where 2[Ba2+] represents the iodate
contributed by the sparingly
soluble Ba(IO3)2 .

2-47
A0.02 M excess of Ba2+ decreases
the solubility of Ba(IO3)2 by a
factor of about five; this same
excess of IO3- lowers the
solubility by a factor of about
200.

2-48
 WritingDissociation Constants
for Acids and Bases

where Ka is the acid dissociation

constant for nitrous acid.

2-49
 Writing Dissociation Constants
for Acids and Bases
◦ In an analogous way, the base
dissociation constant Kb for
ammonia is

2-50
• Dissociation Constants for Conjugate
Acid/Base Pairs

(2-16)
2-51
• Dissociation Constants for Conjugate
Acid/Base Pairs

− To obtain a dissociation constant for a base,

look up in Appendix 2 the dissociation 2-52
 What is Kb for the equilibrium

2-53
• Calculating the Hydronium Ion
Concentration in Solutions of Weak
Acids

2-54
 Calculating the Hydronium Ion
Concentration in Solutions of
Weak Acids
◦ One H3O+ ion is formed for each
A- ion, and we write
(2-17)

(2-18)
2-55
 Calculating
the Hydronium Ion
Concentration in Solutions of
Weak Acids

(2-19)

2-56
 Calculating
the Hydronium Ion
Concentration in Solutions of
Weak Acids

(2-19)

2-57
 Calculating
the Hydronium Ion
Concentration in Solutions of Weak
Acids
(2-20)

(2-21)

(2-
22)
2-58
 Calculatingthe Hydronium Ion
Concentration in Solutions of
Weak Acids
◦ Equation simplified

(2-23)

(2-24)
2-59
 Calculating the Hydronium Ion
Concentration in Solutions of Weak
Acids
◦ The magnitude of the error
introduced by the assumption that
[H3O+] << cHA increases as the
molar concentration of acid
becomes smaller and its
dissociation constant becomes
larger. 2-60
 Calculating the Hydronium Ion
Concentration in Solutions of Weak
Acids
◦ Note that the error introduced by
the assumption is about 0.5%
when the ratio cHA/Ka is 104. The
error increases to about 1.6% when
the ratio is 103, to about 5% when
it is 102, and to about 17% when it
is 10. 2-61
 Calculating
the Hydronium Ion
Concentration in Solutions of Weak
Acids
◦ It is noteworthy that the hydronium
ion concentration computed with the
approximation becomes equal to or
greater than the molar concentration
of the acid when the ratio is unity or
smaller, which is clearly a
meaningless result. 2-62
2-63
 Calculate
the hydronium ion
concentration in 0.120 M nitrous
acid.

2-64
2-65
 [H3O+] << 0.120

We now examine the assumption that 0.120 0.0092

0.120 and see that the error is about 8%. The relative
error in [H3O] is actually smaller than this figure,
however, as we can see by calculating log (cHA/Ka) =
2.2, which, from Figure 2-4, suggests an error of
about 4%. If a more accurate figure is needed,
solution of the quadratic equation yields 8.9 × 103 M
for the hydronium ion concentration. 2-66
 Calculate
the hydronium ion
concentration in a solution that is
2.0 × 10-4 M in anilinium
hydrochloride, C6H5NH3Cl.

2-67
 Theweak acid C6H5NH3+
dissociates as follows:

2-68
 Assume that [H3O+] << 2.0 × 10-4

 Comparison of 7.09 × 10-5 with 2.0

× 10-4 , (This error is about 20%).

2-69
2-70
• Finding the Hydronium Ion
Concentration in Solutions of Weak
Bases

2-71
 Calculatethe hydroxide ion
concentration of a 0.0750 M NH3
solution.

2-72
2-73
 [OH-] << 7.50 × 10-2

the error in [OH-] is less than 2%.

2-74
 Calculate
the hydroxide ion
concentration in a 0.0100 M
sodium hypochlorite solution.

2-75
2-76
2-77
3. What CrO42- concentration is
required to
a) initiate precipitation of Ag2CrO4
from a solution that is 3.41 x 10-2 M
in Ag+ ?
Ksp of Ag2CrO4 = 1.2 x 10-12
b) lower the concentration of Ag+ in a
solution to 2.00 x 10-6 M ?

1-
81
4. At 250C, what are the molar
H3O+ and OH- concentrations in
a) 0.03 M HOCl
b) 0.100 M ethylamine
c) 0.200 M NaOCl
d) 0.25 M hydroxylamine
hydrochloride

1-
82
5. What weight of sodium
formate must be added to 400.0
mL of 1.00 M formic acid to
produce a buffer solution that has
a pH of 3.50?
Note: Use Henderson – Hasselbalch
Equation
pH = pKa + log (CNaA / C HA)
1-
83