CHAPTER

Aqueous Solutions and

Chemical Equilibria
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Electrolytes, which form ions when dissolved in water (or certain
other solvents) and thus produce solutions that conduct electricity.

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 9A-2 Acids and Bases

Brønsted-Lowry? Lewis ?
Conjugate Acids and Bases

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 For example,

water acts as a proton acceptor, or base, in an aqueous

solution of nitrous acid:

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 Possible structures for the hydronium ion.
Figure 9-1

(a) The species H9O4+ has been observed in the solid state and may be an
important contributor in aqueous solution. (b) The species (H2O)21H+
exhibits a dodecahedral caged structure in mixed water-trimethylamine
cluster ions. The hydronium ion (not shown) is encased in the hydrogen-
bonded cage with 10 non-hydrogen-bonded protons protruding from its
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surface. p.230
 The conjugate acid of water is the hydrated proton
written as H3O+. This species is called the hydronium
ion and consists of a proton covalently bonded to one
water molecule.
An acid that has donated a proton becomes a
conjugate base capable of accepting a proton to re-
form the original acid.

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 9A-3 Amphiprotic Species

Species that possess both acidic and basic properties

are amphiprotic. (可吸收或放出質子)

Water is the classic example of an amphiprotic

solvent

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 zwitterion—a species that bears both a positive and a
negative charge. (同時具有正負電, 分子內電荷分離)

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 9A-4 Autoprotolysis 自解離

Amphiprotic solvents undergo self-ionization, or

autoprotolysis, to form a pair of ionic species.
2H2O  H3O+ + OH-
Examples in Page 232

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 9A-5 Strengths of Acids and Bases

Perchloric acid or hydrochloric acid ?

Acetic acid thus acts as a differentiating solvent
Water, on the other hand, is a leveling solvent

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 9B CHEMICAL EQUILIBRIUM

a state of chemical equilibrium in which the ratio of

concentrations of reactants and products is constant.

Equilibrium-constant expressions are algebraic

equations that describe the concentration relationships
existing among reactants and products at equilibrium.
principle of Le Châtelier,

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 9B-2 Equilibrium-Constant Expressions

Consider a generalized equation for a chemical

equilibrium

The equilibrium-constant expression for this reaction

is

the square-bracketed terms :

1. molar concentration if the species is a dissolved solute.
2. partial pressure in atmospheres if the species is a gas

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 if Z in Equation 9-6 is the solvent H2O, the
equilibrium-constant expression simplifies to

The constant K in Equation 9-7 is a temperature-

dependent numerical quantity called the equilibrium
constant.
 The exact expression takes the form

where aY, aZ, aW, and aX are the activities of species Y,

Z,W, and X.

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 Table 9-2

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 FEATURE 9-1
Stepwise and Overall Formation Constants for
Complex Ions
The formation of Ni(CN)42－ (Table 9-2) is typical in
that it occurs in steps as shown.
Note that stepwise formation constants are symbolized
by K1, K2, and so forth.

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 Overall constants are designated by the symbol βn.
Thus,

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 9B-4 Applying the Ion-Product Constant for Water

Aqueous solutions contain small concentrations of

hydronium and hydroxide ions as a consequence of
the dissociation reaction

the new constant Kw is given a special name, the ion-

product constant for water.

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  A useful relationship is obtained by taking the
negative logarithm of Equation 9-11.

By the definition of p-function, (see Section 4B-1)The

exact expression takes the form

At 25°C, pKw =14.00.

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 Feature 9-2

FEATURE 9-2
Why [H2O] Does Not Appear in Equilibrium-Constant
Expressions for Aqueous Solutions
In a dilute aqueous solution, the molar concentration
of water is

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 Suppose we have 0.1 mol of HCl in 1 L of water.
even if all the OH ions are converted to H2O, the
water concentration will increase to only

The percent change in water concentration is

which is certainly inconsequential. Thus, K[H2O]2 in

Equation 9-10 is, for all

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 Table 9-3

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 Example 9-1

EXAMPLE 9-1
Calculate the hydronium and hydroxide ion
concentrations of pure water at 25°C and 100°C.
Because OH－ and H3O+ are formed only from the
dissociation of water, their concentrations must be
equal:
Substitution into Equation 9-11 gives

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 At 25°C,

At 100°C, from Table 9-3,

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 Example 9-2

EXAMPLE 9-2
Calculate the hydronium and hydroxide ion
concentrations and the pH and pOH of 0.200 M
aqueous NaOH at 25°C.
Sodium hydroxide is a strong electrolyte, and its
contribution to the hydroxide ion concentration in this
solution is 0.200 mol/L.

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 where [H3O+] accounts for the hydroxide ions
contributed by the solvent.
The concentration of OH－ from the water is
insignificant, however, when compared with 0.200, so
we can write

Note that the approximation

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 9B-5 Applying Solubility-Product Constants
Most, but not all, sparingly soluble salts are essentially
completely dissociated in saturated aqueous solution.

where the new constant is called the solubility-product

constant or the solubility product.

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 Example 9-3

EXAMPLE 9-3
How many grams of Ba(IO3)2 (487 g/mol) can be
dissolved in 500 mL of water at 25°C?
The solubility-product constant for Ba(IO3)2 is 1.57 ×
-9
10 (see Appendix 2).

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 The mass of Ba(IO3)2 in 500 mL is given by mass
Ba(IO3)2

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 common-ion effect

EXAMPLE 9-4
Calculate the molar solubility of Ba(IO3)2 in a solution
that is 0.0200 M in Ba(NO3)2.

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 強解離 弱解離

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EXAMPLE 9-5
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 .

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 9B-6 Applying Acid-Base Dissociation
Constants

where Ka is the acid dissociation constant for nitrous

acid. In an analogous way, the base dissociation
constant for ammonia is

Note that [H2O] does not appear in the denominator of

either equation because the concentration of water is
so large relative to the concentration of the weak acid
or base that the dissociation does not alter [H2O]
appreciably
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Dissociation Constants for Conjugate Acid/Base Pairs

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歐亞書局 p.243
 Example 9-6

EXAMPLE 9-6
What is Kb for the equilibrium

Appendix 3 lists a Ka value of 6.2 × 10 -10

for HCN.
Thus,

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 Hydronium Ion Concentration of Solutions of Weak
Acids
When the weak acid HA is dissolved in water, two
equilibria are established that yield hydronium ions:

Under these circumstances, one H3O+ ion is formed

for each A－ion, and we write

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 Substituting [H3O+] for [A－] (see Equation 9-15) into
Equation 9-16 yields

which rearranges to

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 which rearranges to

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 provided [H3O+] ＜＜ cHA, cHA－ [H3O+] ≈ cHA, and
Equation 9-18 reduces to

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.

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 Table 9-4

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 Example 9-7

EXAMPLE 9-7
Calculate the hydronium ion concentration in 0.120 M
nitrous acid.
The principal equilibrium is

for which (see Appendix 2)

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 Substitution into Equations 9-15 and 9-17 gives

When these relationships are introduced into the

expression for Ka, we obtain

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 If we now assume that [H3O+] ＜＜ 0.120, we find

We now examine the assumption that 0.120－0.0092

≈ 0.120 and see that the error is about 8%.

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 Example 9-8

EXAMPLE 9-8
Calculate the hydronium ion concentration in a
solution that is 2.0×10-4 M in aniline hydrochloride,
C6H5NH3Cl.
In aqueous solution, dissociation of the salt to Cl－ and
C6H5NH3+ is complete.
The weak acid C6H5NH3+ dissociates as follows:

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 If we look in Appendix 3, we find that the Ka for
C6H5NH3+ is 2.51 × 10-5.
Proceeding as in Example 9-7, we have

Assume that [H3O+] ＜＜ 2.0×10-4, and substitute the

simplified value for [C6H5NH3+ ] into the dissociation-
constant expression to obtain (see Equation 9-21)

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 7.09 × 10-5 vs. 2.0 × 10-4 [H3O+] ＜＜ . 不成
立
使用詳解

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 Hydronium Ion Concentration of Solutions of Weak Bases

Aqueous ammonia is basic by virtue of the reaction

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 Example 9-9

EXAMPLE 9-9
Calculate the hydroxide ion concentration of a 0.0750
M NH3 solution.
The predominant equilibrium is

As shown on page 243.

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 The chemical equation shows that

Both NH4+ and NH3 come from the 0.0750 M

solution. Thus,

If we substitute [OH－] for [NH4+] in the second of

these equations and rearrange, we find that

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 Substituting these quantities into the dissociation-
constant expression yields

which is analogous to Equation 9-17 for weak acids.

Provided that [OH－] ＜＜ 7.50 × 10-2, this equation
simplifies to

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 Comparing the calculated value for [OH－] with 7.50
× 10-2, we see that the error in [OH－] is less than 2%.
If needed, a better value for [OH－] can be obtained by
solving the quadratic equation.

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 9C BUFFER SOLUTIONS

By definition, a buffer solution resists changes in pH

with dilution or with addition of acids or bases.
buffer solutions are prepared from a conjugate
acid/base pair
Chemists use buffers to maintain the pH of solutions
at a relatively constant and predetermined level.

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 9C-1 Calculation of the pH of Buffer Solutions

A solution containing a weak acid, HA, and its

conjugate base, A－

Their analytical concentrations, cHA and cNaA

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 Buffer capacity 夠 = mole 數高
使用弱酸 or 弱鹼共軛系統
接近中性 pH = 5~9

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 FEATURE 9-5

FEATURE 9-5
The Henderson-Hasselbalch Equation
The Henderson-Hasselbalch equation, which is used
to calculate the pH of buffer solutions

Therefore,

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 EXAMPLE 9-11

EXAMPLE 9-11
What is the pH of a solution that is 0.400 M in formic
acid and 1.00 M in sodium formate?
The pH of this solution will be affected by the Kw of
formic acid and the Kb of formate ion.

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 Since the Ka for formic acid is orders of magnitude
larger than the Kb for formate, the solution will be
acidic and Ka will determine the H3O+ concentration.
We can thus write

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 Substitution into Equation 9-29 gives, with
rearrangement,

Note that the assumption that [H3O+] ＜＜ cHCOOH and

that [H3O+] ＜＜ cHCOO－ is valid. Thus,

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 EXAMPLE 9-12

EXAMPLE 9-12
Calculate the pH of a solution that is 0.200 M in NH3
and 0.300 M in NH4Cl.
In Appendix 3, we find that the acid dissociation
constant Ka for NH4+ is 5.70 × 10-10.
The equilibria we must consider are

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 Using the arguments that led to Equations 9-25 and 9-
26, we obtain

Because Kb is several orders of magnitude larger than

Ka, we have assumed that the solution is basic and that
[OH－] is much larger than [H3O+].
Thus, we have neglected the concentration of H3O+ in
these approximations.

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 Also assume that [OH－] is much smaller than
and so that

Substituting into the acid dissociation constant for

NH4+, we obtain a relationship similar to Equation 9-
29. That is,

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 To check the validity of our approximations, we
calculate [OH－]. Thus,

which is certainly much smaller than or .

Thus, we may write

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 9C-2 Properties of Buffer Solutions

The Effect of Dilution

The Effect of Added Acids and Bases

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 EXAMPLE 9-13

EXAMPLE 9-13
Calculate the pH change that takes place when a
100-mL portion of (a) 0.0500 M NaOH and (b)
0.0500 M HCl is added to 400 mL of the buffer
solution that was described in Example 9-12.
(a) Addition of NaOH converts part of the NH4+ in the
buffer to NH3:

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 The analytical concentrations of NH3 and NH4Cl then
become

When substituted into the acid dissociation-constant

expression for NH4+, these values yield

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 and the change in pH is

(b) Addition of HCl converts part of the NH3 to NH4+;

thus,

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 The Composition of Buffer Solutions as a Function of
pH; Alpha Values

We then define α0, the fraction of the total

concentration of acid that is undissociated, as

and α1, the fraction dissociated, as

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 Alpha values are unitless ratios whose sum must equal
unity. That is,

Alpha values depend only on [H3O+] and Ka and are

independent of cT.
we rearrange the dissociation-constant expression to

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 On rearrangement, we obtain

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 But by definition, [HOAc]/cT = α0

To obtain an expression for α1, we rearrange the

dissociation-constant expression to

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 Buffer Capacity
The ability of a buffer to prevent a significant change
in pH is directly related to the total concentration of
the buffering species as well as to their concentration
ratio.
The buffer capacity, β, of a solution is defined as the
number of moles of a strong acid or a strong base that
causes 1.00 L of the buffer to undergo a 1.00-unit
change in pH.

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 Figure 9-5
Figure 9-5
Variation in α with
pH. Note that most
of the transition
between α0 and α1
occurs within ± 1
pH unit of the
crossover point of
the two curves. The
crossover point
whereα0=α1=0.5
occurs when pH =
pKHOAc=4.74.

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 Figure 9-6 Figure 9-6
Buffer capacity as a
function of the
logarithm of the ratio
cNaA/cHA. The
maximum buffer
capacity occurs when
the concentration of
acid and conjugate
base are equal; that
is, when α0=α1=0.5.

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 EXAMPLE 9-14

EXAMPLE 9-14
Describe how you might prepare approximately
500.0 mL or a pH 4.5 buffer solution from 1.0 M
acetic acid (HOAc) and sodium acetate (NaOAc).
The H3O+ concentration should be

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 The acetate concentration should be

The mass of NaOAc needed is then

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