Question If you want to know whether a exceeded precipitates along with another substance whose solubility is exceeded.

exceeded. For exam-

small amount of Pb2ⴙ coprecipitates with
Hg2I2, should you measure the Pb2ⴙ concen-
tration in the mother liquor (the solution) or
the Pb2ⴙ concentration in the precipitate?
Which measurement is more sensitive? By
“sensitive,” we mean responsive to a small
amount of coprecipitation. (Answer: Measure
Pb2ⴙ in precipitate.)
ple, some Pb2 might become adsorbed on the surface of the Hg2I2 crystal or might even
occupy sites within the crystal. Our calculation says that the separation is worth trying. Only
an experiment can show whether the separation actually works.
6-4 Complex Formation
If anion X precipitates metal M, it is often observed that a high concentration of X causes


solid MX to redissolve. The increased solubility arises from formation of complex ions, such
as MX 2 , which consist of two or more simple ions bonded to one another.

Lewis Acids and Bases

In complex ions such as PbI, PbI 2 2
3 , and PbI4 , iodide is said to be the ligand of Pb . A
2
ligand is any atom or group of atoms attached to the species of interest. We say that Pb acts
as a Lewis acid and I acts as a Lewis base in these complexes. A Lewis acid accepts a pair
of electrons from a Lewis base when the two form a bond:

: :
: :

Lewis acid ⴙ Lewis base Δ adduct Pb : I: B 关Pb I : 兴
Electron pair Electron pair
acceptor donor Room to A pair of
accept electrons to
electrons be donated

The product of the reaction between a Lewis acid and a Lewis base is called an adduct. The
bond between a Lewis acid and a Lewis base is called a dative or coordinate covalent bond.

Effect of Complex Ion Formation on Solubility12

If Pb2 and I only reacted to form solid PbI2, then the solubility of Pb2 would always be
very low in the presence of excess I:
Ksp
PbI2(s) Δ Pb2  2I Ksp  [Pb2 ][I ]2  7.9 109 (6-11)

We observe, however, that high concentrations of I cause solid PbI2 to dissolve. We explain
this by the formation of a series of complex ions:
K1
Notation for these equilibrium constants is Pb2  I Δ PbI K1  [PbI ]/[Pb2 ][I ]  1.0 102 (6-12)
discussed in Box 6-2.  2  2
Pb2
 2I Δ PbI2(aq) 2  [PbI2 (aq) ]/ [Pb 2
] [I ]  1.4 3
10 (6-13)
Pb2  3I Δ PbI  [PbI ][I  ]3  8.3
3 2
3 3 3 ]/[Pb 103 (6-14)

][I ]4
4
Pb2
 4I Δ PbI2
4 4  [PbI2
4 ]/[Pb
2
 3.0 10 4
(6-15)
The species PbI2(aq) in Reaction 6-13 is dissolved PbI2, containing two iodine atoms bound
to a lead atom. Reaction 6-13 is not the reverse of Reaction 6-11, in which the species is
solid PbI2.

B OX 6 - 2 Notation For Formation Constants

Formation constants are the equilibrium constants for complex ion The overall, or cumulative, formation constants are denoted i:
formation. The stepwise formation constants, designated Ki, are M  2X Δ MX2
2
 [MX2 ]/ [M] [X] 2
2
defined as follows: n
K1 M  nX Δ MXn n  [MXn ]/ [M] [X] n
M  X Δ MX K1  [MX]/ [M] [X]
K2 A useful relation is that n = K1K2 p Kn. Some formation constants
MX  X Δ MX2 K2  [MX2 ]/ [MX] [X] can be found in Appendix I.
Kn
MXn1  X Δ MXn Kn  [MXn ]/ [MXn1 ] [X]

At low I concentrations, the solubility of lead is governed by precipitation of PbI2(s). At

high I concentrations, Reactions 6-12 through 6-15 are driven to the right (Le Châtelier’s
principle), and the total concentration of dissolved lead is considerably greater than that of
Pb2 alone (Figure 6-3).
A most useful characteristic of chemical equilibrium is that all equilibria are satisfied
simultaneously. If we know [I], we can calculate [Pb2] by substituting the value of [I] into

124 CHAPTER 6 Chemical Equilibrium

 −1

Governed by
common ion
−2 effect
Governed by
complex
formation
−3

log[total Pb concentration]
[Pb]total
−4 [PbI+]

−5

[PbI2(aq)]

−6

[PbI3– ]
[Pb2+]
−7
–
[PbI42 ]

−8
−3.0 −2.0 −1.0 0.0 1.0
log[I–]

FIGURE 6-3 Total solubility of lead(II) (curve with circles) and solubilities of individual species
(straight lines) as a function of the concentration of free iodide. To the left of the minimum, [Pb]total is
governed by the solubility product for PbI2(s). As [Iⴚ] increases, [Pb]total decreases because of the
common ion effect. At high values of [Iⴚ], PbI2(s) redissolves because it reacts with Iⴚ to form soluble
complex ions, such as PbI42ⴚ. Note logarithmic scales. The solution is made slightly acidic so that
[PbOHⴙ] is negligible.

the equilibrium constant expression for Reaction 6-11, regardless of whether there are other
reactions involving Pb2. The concentration of Pb2 that satisfies any one equilibrium must
satisfy all equilibria. There can be only one concentration of Pb2 in the solution.

EXAM PLE Effect of I⫺ on the Solubility of Pb2⫹

Find the concentrations of PbI, PbI2(aq), PbI 2
3 , and PbI4 in a solution saturated with

PbI2(s) and containing dissolved I with a concentration of (a) 0.001 0 M and (b) 1.0 M.

Solution (a) From Ksp for Reaction 6-11, we calculate

[Pb2 ]  Ksp/ [I ] 2  (7.9 109 )/(0.001 0) 2  7.9 103 M
From Reactions 6-12 through 6-15, we then calculate the concentrations of the other lead-
containing species:
[PbI  ]  K1[Pb2[I ]  (1.0 102 )(7.9 103 )(1.0 103 )
4
 7.9 10 M
 2 5
[ PbI2(aq)]  2[Pb
2
][I ]  1.1 10 M
[PbI
3 ]  3[Pb
2
][I ]3  6.6 108 M
4 ] 
[PbI2 4[Pb
2
][I ]4  2.4 1010 M
(b) If, instead, we take [I ]  1.0 M, then analogous computations show that
[Pb2 ]  7.9 109 M [PbI
3 ]  6.6 105 M
 7
[PbI ]  7.9 10 M [PbI2
4 ]  2.4 104 M
5
[PbI2(aq)]  1.1 10 M

Test Yourself Find [Pb2], [PbI2(aq)], and [PbI3 ], in a saturated solution of PbI2(s)
with [I]  0.10 M. (Answer: 7.9 107, 1.1 105, 6.6 106 M)

6-4 Complex Fraction 125


The effect of dissolved ions on chemical
equilibria is the subject of Chapter 7.
Brønsted-Lowry acid: proton donor
Brønsted-Lowry base: proton acceptor
J. N. Brønsted (1879–1947) of the University of
Copenhagen and T. M. Lowry (1874–1936) of
Cambridge University independently
published their definitions of acids and bases
in 1923.
126
The total concentration of dissolved lead in the preceding example is
[Pb] total  [Pb2]  [PbI]  [PbI2 (aq) ]  [PbI
3 ]  [PbI4 ]
2
When [I] = 103 M, [Pb]total = 8.7 103 M, of which 91% is Pb2. As [I] increases,
[Pb]total decreases by the common ion effect operating in Reaction 6-11. However, at sufficiently
high [I], complex formation takes over and [Pb]total increases in Figure 6-3. When [I] 
1.0 M, [Pb]total  3.2 104 M, of which 76% is PbI2 4 .
Tabulated Equilibrium Constants Are Usually Not “Constant”
If you look up the equilibrium constant of a chemical reaction in two different books, there is
an excellent chance that the values will be different (sometimes by a factor of 10 or more).13
This discrepancy occurs because the constant may have been determined under different
conditions and, perhaps, by using different techniques.
A common source of variation in the reported value of K is the ionic composition of the
solution. Note whether K is reported for a particular ionic composition (for example, 1 M
NaClO4) or whether K has been extrapolated to zero ion concentration. If you need an equi-
librium constant for your own work, choose a value of K measured under conditions as close
as possible to those you will employ.
6-5 Protic Acids and Bases
Understanding the behavior of acids and bases is essential to every branch of science having
anything to do with chemistry. In analytical chemistry, we almost always need to account for
the effect of pH on analytical reactions involving complex formation or oxidation-reduction.
pH can affect molecular charge and shape—factors that help determine which molecules can
be separated from others in chromatography and electrophoresis and which molecules will be
detected in some types of mass spectrometry.
In aqueous chemistry, an acid is a substance that increases the concentration of H3O
(hydronium ion) when added to water. Conversely, a base decreases the concentration of
H3O. We will see that a decrease in H3O concentration necessarily requires an increase
in OH concentration. Therefore, a base increases the concentration of OH in aqueous
solution.
The word protic refers to chemistry involving transfer of H from one molecule to an-
other. The species H is also called a proton because it is what remains when a hydrogen atom
loses its electron. Hydronium ion, H3O, is a combination of H with H2O. Although H3O
is a more accurate representation than H for the hydrogen ion in aqueous solution, we will
use H3O and H interchangeably in this book.
Brønsted-Lowry Acids and Bases
Brønsted and Lowry classified acids as proton donors and bases as proton acceptors. HCl is
an acid (a proton donor), and it increases the concentration of H3O in water:
HCl  H2O Δ H3O  Cl
The Brønsted-Lowry definition does not require that H3O be formed. This definition can
therefore be extended to nonaqueous solvents and to the gas phase:
 
HCl(g)  NH3 (g) Δ NH 4 Cl (s)
Hydrochloric acid Ammonia Ammonium chloride
(acid) (base) (salt)
For the remainder of this book, when we speak of acids and bases, we are speaking of
Brønsted-Lowry acids and bases.
Salts
Any ionic solid, such as ammonium chloride, is called a salt. In a formal sense, a salt
can be thought of as the product of an acid-base reaction. When an acid and a base react,
they are said to neutralize each other. Most salts containing cations and anions with
single positive and negative charges are strong electrolytes—they dissociate nearly com-
pletely into ions in dilute aqueous solution. Thus, ammonium chloride gives NH4 and
Cl in water:
NH4 Cl(s) S NH4 (aq)  Cl(aq)
CHAPTER 6 Chemical Equilibrium
Conjugate Acids and Bases
The products of a reaction between an acid and a base are also classified as acids and
bases:

⬊ ⬊ Conjugate acids and bases are related by the

O ⬊ O ⬊ H
gain or loss of one proton. In these structures,
T

⬊
CH3 C  CH3 N CH3 C  CH3 N a solid wedge is a bond coming out of the
⬊ H ⬊ H plane of the page and a dashed wedge is a

⬊ O H H ⬊ O H bond to an atom behind the page.

⬊
Acetic acid Methylamine Acetate ion Methylammonium ion

Acid Base Base Acid

Conjugate pair

Conjugate pair

Acetate is a base because it can accept a proton to make acetic acid. Methylammonium ion is
an acid because it can donate a proton and become methylamine. Acetic acid and the acetate
ion are said to be a conjugate acid-base pair. Methylamine and methylammonium ion are
102
likewise conjugate. Conjugate acids and bases are related to each other by the gain or loss pm
of one H.

The Nature of H⫹ and OH⫺

110
The proton does not exist by itself in water. The simplest formula found in some crystalline °

salts is H3O. For example, crystals of perchloric acid monohydrate contain pyramidal 17
2p
hydronium (also called hydroxonium) ions: m

 
O
Eigen structure of H3Oⴙ
⬊

HClO4 • H2O is really O Cl FIGURE 6-4 Structure of hydronium ion,

H O H3Oⴙ, proposed by M. Eigen and found in
H O
H O many crystals.14 The bond enthalpy (heat
needed to break the OH bond) of H3Oⴙ is
Hydronium Perchlorate 544 kJ/mol, about 84 kJ/mol greater than the
bond enthalpy in H2O.
The formula HClO4 H2O is a way of specifying the composition of the substance when we
are ignorant of its structure. A more accurate formula would be H3OClO4.
Average dimensions of the H3O cation in many crystals are shown in Figure 6-4. In
aqueous solution, H3O is tightly associated with three molecules of water through excep-
tionally strong hydrogen bonds (Figure 6-5). The H5O2 cation is another simple species in
which a hydrogen ion is shared by two water molecules.16,17 252 pm

H H •••••
••••••

Zundel structure of
•••

O • • • H • • • O (H3O ⴢ H2O)
H b 243 pm B H

In the gas phase, H3O can be surrounded by 20 molecules of H2O in a regular dodeca-
hedron held together by 30 hydrogen bonds.18 In a salt containing the discrete cation FIGURE 6-5 Environment of aqueous
(C6H6)3H3O, and in benzene solution, hydrogen atoms of the pyramidal H3O ion are each H3O⫹.14 Three H2O molecules are bound to
H3O⫹ by strong hydrogen bonds (dotted
attracted toward the center of the pi electron cloud of a benzene ring (Figure 6-6).
lines), and one H2O (at the top) is held by
The ion H3O2 (OHⴢH2O) has been observed by X-ray crystallography.19 The central
weaker ion-dipole attraction (dashed line).
O H p O linkage contains the shortest hydrogen bond involving H2O that has ever been
p
The O ¬ H p O hydrogen-bonded distance of
observed. 252 pm (picometers, 10⫺12 m) compares with
an O ¬ H p O distance of 283 pm between
H hydrogen-bonded water molecules. The discrete
cation (H2O)3H3O⫹ found in some crystals is
O H O
similar in structure to (H2O)4H3O⫹, with the
H b 229 pm B weakly bonded H2O at the top removed.15

6-5 Protic Acids and Bases 127

FIGURE 6-6 H3O⫹ ⴢ 3C6H6 cation found in
the crystal structure of [(C6H6)3H3O⫹]
[CHB11Cl11⫺]. [From E. S. Stoyanov, K.-C. Kim, and
C. A. Reed, “The Nature of the H3O Hydronium Ion
in Benzene and Chlorinated Hydrocarbon Solvents,”
J. Am. Chem. Soc. 2006, 128, 1948.]

We will ordinarily write H in most chemical equations, although we really mean H3O.
To emphasize the chemistry of water, we will write H3O. For example, water can be either
an acid or a base. Water is an acid with respect to methoxide:
⬊ ⬊

⬊ ⬊

⬊ ⬊

⬊ ⬊
H O H  CH3 O T H O  CH3 O H
Water Methoxide Hydroxide Methanol

But with respect to hydrogen bromide, water is a base:

H2O  HBr Δ H3O  Br
Water Hydrogen Hydronium Bromide
bromide ion

Autoprotolysis
Water undergoes self-ionization, called autoprotolysis, in which it acts as both an acid and a
base:
H2O  H2O Δ H3O  OH (6-16)
or
We will write Hⴙ when we really mean H3Oⴙ. H2O Δ H  OH (6-17)
Reactions 6-16 and 6-17 mean the same thing.
Protic solvents have a reactive H, and all protic solvents undergo autoprotolysis. An
example is acetic acid:
Examples of protic solvents (acidic proton O O
OH
bold): ™ 
™
H2O CH3CH2OH 2CH3COH—T—CH3C ———CH3C ® O——
(in acetic acid) (6-18)
Water Ethanol OH
Examples of aprotic solvents (no acidic The extent of these reactions is very small. The autoprotolysis constants (equilibrium con-
protons): stants) for Reactions 6-17 and 6-18 are 1.0 1014 and 3.5 1015, respectively, at 25C.
CH3CH2OCH2CH3 CH3CN
Diethyl ether Acetonitrile
6-6 pH
The autoprotolysis constant for H2O has the special symbol Kw, where “w” stands for water:
Recall that H2O (the solvent) is omitted Autoprotolysis Kw
from the equilibrium constant. The value of water: H2O Δ H  OH Kw  [H ][OH ] (6-19)
Kw ⴝ 1.0 ⴛ 10ⴚ14 at 25ⴗC is accurate
enough for problems in this book. Table 6-1 shows how Kw varies with temperature. Its value at 25.0C is 1.01 1014.

128 CHAPTER 6 Chemical Equilibrium

 TABLE 6-1 Temperature dependence of Kwa

Temperature (ⴗC) Kw pKw = ⴚlog Kw Temperature (ⴗC) Kw pKw ⴝ ⴚlog Kw

0 1.15 1015 14.938 40 2.88 1014 13.541
5 1.88 1015 14.726 45 3.94 1014 13.405
10 2.97 1015 14.527 50 5.31 1014 13.275
15 4.57 1015 14.340 100 5.43 1013 12.265
20 6.88 1015 14.163 150 2.30 1012 11.638
25 1.01 1014 13.995 200 5.14 1012 11.289
30 1.46 1014 13.836 250 6.44 1012 11.191
35 2.07 1014 13.685 300 3.93 1012 11.406
a. Concentrations in the product [H][OH] in this table are expressed in molality rather than in molarity. Accuracy of log Kw is 0.01. To convert molality (mol/kg) into molarity (mol/L),
multiply by the density of H2O at each temperature. At 25 C, Kw  1013.995 (mol/kg) 2(0.997 05 kg/L)2  1013.998(mol/L) 2.
SOURCE: W. L. Marshall and E. U. Franck, “Ion Product of Water Substance, 0–1 000C, 1–10,000 Bars,” J. Phys. Chem. Ref. Data 1981, 10, 295. For values of Kw over a temperature range
of 0 – 800C and a density range of 0–1.2 g/cm3, see A. V. Bandura and S. N. Lvov, “The Ionization Constant of Water over Wide Ranges of Temperature and Pressure,” J. Phys. Chem. Ref.
Data 2006, 35, 15.

EXAM PLE Concentration of H⫹ and OH⫺ in Pure Water at 25ⴗC

Calculate the concentrations of H and OH in pure water at 25C.

Solution The stoichiometry of Reaction 6-19 tells us that H and OH are produced in a 1:1
molar ratio. Their concentrations must be equal. Calling each concentration x, we can write
Kw  1.0 1014  [H ] [OH ]  [x] [ x] 1 x  1.0 107 M
The concentrations of H and OH are both 1.0 107 M in pure water.

Test Yourself Use Table 6-1 to find the [H] in water at 100C and at 0C. (Answer:
7.4 107 and 3.4 108 M)

EXAM PLE Concentration of OHⴚ When [Hⴙ] Is Known

What is the concentration of OH if [H]  1.0 103 M? (From now on, assume that
the temperature is 25C unless otherwise stated.)

Solution Putting [H]  1.0 103 M into the Kw expression gives

Kw  1.0 1014  (1.0 103 )[OH ] 1 [OH ]  1.0 1011 M
A concentration of [H]  1.0 103 M gives [OH]  1.0 1011 M. As the concen-
tration of H increases, the concentration of OH necessarily decreases, and vice versa.
A concentration of [OH]  1.0 103 M gives [H]  1.0 1011 M.

Test Yourself Find [OH] if [H]  1.0 104 M. (Answer: 1.0 1010 M)

An approximate definition of pH is the negative logarithm of the H concentration.

Approximate definition of pH: pH ⬇ log[H ] (6-20) pH ⬇ log [Hⴙ]. The term “pH” was introduced
Chapter 7 defines pH more accurately in terms of activities, but, for many purposes, Equation in 1909 by the Danish biochemist S. P. L.
Sørensen, who called it the “hydrogen ion
6-20 is a good definition. The measurement of pH with glass electrodes, and buffers used by
exponent.”20
the U.S. National Institute of Standards and Technology to define the pH scale, are described
in Chapter 14.
In pure water at 25C with [H]  1.0 107 M, the pH is –log(1.0 107)  7.00.
If [OH]  1.0 103 M, then [H]  1.0 1011 M and the pH is 11.00. A useful relation Take the log of both sides of the Kw expression
to derive Equation 6-21:
between [H] and [OH] is
Kw ⴝ [Hⴙ][OHⴚ ]
pH  pOH  log(Kw )  14.00 at 25°C (6-21)
log Kw ⴝ log[Hⴙ] ⴙ log[OHⴚ ]
 
where pOH  –log[OH ], just as pH  –log[H ]. Equation 6-21 is a fancy way of saying that ⴚlog Kw ⴝ ⴚlog[Hⴙ] ⴚ log[OHⴚ]
if pH  3.58, then pOH  14.00 – 3.58  10.42, or [OH]  1010.42  3.8 1011 M. 14.00 ⴝ pH ⴙ pOH (at 25ⴗC)

6-6 pH 129
FIGURE 6-7 pH of various substances. [From Baking soda
Chem. Eng. News, 14 September 1981.] The most Lake Ontario
acidic rainfall (Box 14-1) is a stronger acid than Human urine Alkaline
lemon juice. The most acidic natural waters Saliva, pH 5.7–7.1
known are mine waters, with total dissolved
Tomato juice 14
13
metal concentrations of 200 g/L and sulfate 12
Average pH of rainfall, 11 Lye
concentrations of 760 g/L.22 The pH of this water, 10
Toronto, February 1979
–3.6, does not mean that [Hⴙ] ⴝ 103.6 M ⴝ 8
9 Ammonia
Apples
4 000 M! It means that the activity of Hⴙ 7 Milk of magnesia
Lemon juice 6
(discussed in Chapter 7) is 103.6. 5 Seawater
Acidic 4
3 Human blood
2
1 Neutral
0
–1 Milk
–2 Theoretical “pure” rain, pH 5.6
–3
Most fish species die, pH 4.5–5.0
Vinegar
Most acidic rainfall recorded in U.S. at Wheeling, W. Va.
Battery acid
Acidic mine water, Iron Mountain, Calif.

A solution is acidic if [H]  [OH]. A solution is basic if [H] [OH]. At 25C, an

acidic solution has a pH below 7 and a basic solution has a pH above 7.
1 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
pH is measured with a glass electrode pH
b ∫∫B b ∫∫B

∫∫B
described in Chapter 14. Acidic Basic
The surface of water or ice is ~2 pH units
more acidic than the bulk because H3Oⴙ is Neutral
more stable on the surface. Surface acidity
could be important to the chemistry of pH values for various common substances are shown in Figure 6-7.
atmospheric clouds.21 Although pH generally falls in the range 0 to 14, these are not the limits of pH. A pH of –1,
for example, means –log[H]  –1; or [H]  10 M. This concentration is attained in a con-
centrated solution of a strong acid such as HCl.

Is There Such a Thing as Pure Water?

TABLE 6-2 Common strong In most labs, the answer is “No.” Pure water at 25C should have a pH of 7.00. Distilled wa-
acids and bases ter from the tap in most labs is acidic because it contains CO2 from the atmosphere. CO2 is
an acid by virtue of the reaction
Formula Name 
CO2  H2O Δ HCO3  H (6-22)
Acids Bicarbonate
HCl Hydrochloric acid CO2 can be largely removed by boiling water and then protecting it from the atmosphere.
(hydrogen chloride) More than a century ago, careful measurements of the conductivity of water were made
HBr Hydrogen bromide by F. Kohlrausch and his students. To remove impurities, they found it necessary to distill
HI Hydrogen iodide water 42 consecutive times under vacuum to reduce conductivity to a limiting value.
H2SO4a Sulfuric acid
HNO3 Nitric acid
HClO4 Perchloric acid 6-7 Strengths of Acids and Bases
Bases Acids and bases are commonly classified as strong or weak, depending on whether they react
LiOH Lithium hydroxide nearly “completely” or only “partially” to produce H or OH. Although there is no sharp
NaOH Sodium hydroxide distinction between weak and strong, some acids or bases react so completely that they are
KOH Potassium hydroxide easily classified as strong—and, by convention, everything else is termed weak.
RbOH Rubidium hydroxide
CsOH Cesium hydroxide
Strong Acids and Bases
R4NOHb Quaternary ammonium Common strong acids and bases are listed in Table 6-2, which you need to memorize. By
hydroxide definition, a strong acid or base is completely dissociated in aqueous solution. That is, the
equilibrium constants for the following reactions are large.
a. For H2SO4, only the first proton ionization is complete.
Dissociation of the second proton has an equilibrium HCl(aq) Δ H  Cl
constant of 1.0 102.
b. This is a general formula for any hydroxide salt of an
KOH(aq) Δ K  OH
ammonium cation containing four organic groups. An
example is tetrabutylammonium hydroxide: Virtually no undissociated HCl or KOH exists in aqueous solution. Demonstration 6-2 shows
(CH3CH2CH2CH2)4N⫹OH. a consequence of the strong-acid behavior of HCl.

130 CHAPTER 6 Chemical Equilibrium

 D E M O N ST R AT I O N 6 - 2 The HCl Fountain

The complete dissociation of HCl into H and Cl makes HCl(g) tube leading to a source of HCl(g) and its outlet tube directed into
extremely soluble in water. an inverted bottle of water. As HCl is admitted to the flask, air is dis-
placed. When the bottle is filled with air, the flask is filled mostly
HCl(g) Δ HCl(aq) (A)
 
with HCl(g).
HCl(aq) Δ H (aq)  Cl (aq) (B) The hoses are disconnected and replaced with a beaker of indi-
  cator and a rubber bulb (Figure b). For an indicator, we use slightly
Net reaction: HCl(g) Δ H (aq)  Cl (aq) (C)
alkaline, commercial methyl purple solution, which is green above
Because the equilibrium of Reaction B lies far to the right, it pulls pH 5.4 and purple below pH 4.8. When ~1 mL of water is squirted
Reaction A to the right as well. from the rubber bulb into the flask, a vacuum is created and indica-
Challenge The standard free energy change (G) for tor solution is drawn up into the flask, making a fascinating fountain
Reaction C is 36.0 kJ/mol. Show that the equilibrium (Color Plate 1).
constant is 2.0 106. Question Why is a vacuum created when water is squirted
The extreme solubility of HCl(g) in water is the basis for the into the flask, and why does the indicator change color when
HCl fountain,23 assembled as shown below. In Figure a, an inverted it enters the flask?
250-mL round-bottom flask containing air is set up with its inlet

Constriction

250-mL
round-bottom
flask

Glass
tubes
Rubber
stopper

2-mL
Beaker containing
250-mL rubber bulb
your favorite
bottle Hoses
indicator

HCl(g) in
from tank

(a) Water (b)

Even though the hydrogen halides HCl, HBr, and HI are strong acids, HF is not a strong TABLE 6-3 Equilibria of alkaline
acid, as explained in Box 6-3. For most purposes, the hydroxides of the alkaline earth metals earth metal hydroxides
(Mg2, Ca2, Sr2, and Ba2) can be considered to be strong bases, although they are far less
soluble than alkali metal hydroxides and have some tendency to form MOH complexes M(OH) 2 (s) Δ M 2  2OH
(Table 6-3). The strongest known base is the gas-phase molecule LiO.25 Ksp  [M2 ] [OH ] 2
M2  OH Δ MOH 
Weak Acids and Bases
K1  [MOH ]/ [M2 ] [OH ]
All weak acids, denoted HA, react with water by donating a proton to H2O:
Ka Metal log Ksp log K1
Dissociation of weak acid: HA  H2O Δ H3O  A (6-23)
Mg2 11.15 2.58
which means exactly the same as
Ca2 5.19 1.30
Sr2 — 0.82
Dissociation of Ka [H ][A ] Ba2 — 0.64
weak acid: HA Δ H  A Ka  (6-24)
[HA]
NOTE: 25C and ionic strength  0.

The equilibrium constant is called Ka, the acid dissociation constant. By definition, a weak [Hⴙ][Aⴚ]
Acid dissociation constant: Ka ⴝ .
acid is one that is only partially dissociated in water, so Ka is “small.” [HA]

6-7 Strengths of Acids and Bases 131

 B OX 6 - 3 The Strange Behavior of Hydrofluoric Acid14
The hydrogen halides HCl, HBr, and HI are all strong acids, which Ion pairs are common in aqueous solutions of any ion with a charge
means that the reactions greater than 1. Ion pairs are the rule in nonaqueous solvents, which
cannot promote ion dissociation as well as water.
HX(aq)  H2O S H3O   X
Thus, HF does not behave as a strong acid because F and
(X  Cl, Br, I) all go to completion. Why, then, does HF behave as H3O remain associated with each other. Dissolving one mole of the
a weak acid? strong acid HCl in water creates one mole of free H3O. Dissolving
The answer is odd. First, HF does completely give up its proton one mole of the “weak” acid HF in water creates little free H3O.
to H2O: HF is not unique in its propensity to form ion pairs. Many
moderately strong acids, such as those below, are thought to exist
HF(aq) S H3O  F predominantly as ion pairs in aqueous solution (HA  H2O Δ
A p H3O) .24
Hydronium Fluoride
ion ion
O OH
But fluoride forms the strongest hydrogen bond of any ion. The hy-
dronium ion remains tightly associated with F through a hydrogen
bond. We call such an association an ion pair.
CF3CO2H O OH
H3O  F Δ F p H3O Trifluoroacetic acid Squaric acid
An ion pair Ka  0.31 Ka  0.29

Weak bases, B, react with water by abstracting a proton from H2O:

Base Kb [BH ][OH ]

[ BHⴙ] [ OHⴚ ] B  H2O Δ BH  OH Kb  (6-25)
Base hydrolysis constant: Kb ⴝ hydrolysis: B
[B]
Hydrolysis refers to any reaction with water. The equilibrium constant Kb is the base hydrolysis constant, which is “small” for a weak base.

Common Classes of Weak Acids and Bases

Acetic acid is a typical weak acid.
O O
CH3 C T CH3 C  H Ka  1.75 105 (6-26)

O H O
Acetic acid Acetate
(HA) (A)

Acetic acid is a representative carboxylic acid, which has the general formula RCO2H, where
R is an organic substituent. Most carboxylic acids are weak acids, and most carboxylate
anions are weak bases.
O O
R C R C
O H O
A carboxylic acid A carboxylate anion
(weak acid, HA) (weak base, A)
Methylamine is a typical weak base.
H
å
N  H2O T N ——OH—— Kb  4.47 104 (6-27)
CH3 œ CH3 œ
Carboxylic acids (RCO2H) and ammonium H— — H
ions (R3NHⴙ) are weak acids. H H
Carboxylate anions (RCOⴚ
2 ) and amines (R3N) Methylamine Methylammonium ion
are weak bases. B BH
Amines are nitrogen-containing compounds:

¨ 2
14243

RNH a primary amine RNH 3


¨
R2NH a secondary amine R2NH 2 ammonium ions

¨
R3N a tertiary amine R3NH

132 CHAPTER 6 Chemical Equilibrium

 Li+ Be
13.64

Na+ Mg2+ Stronger acid Al3+

13.9 11.4 5.00

K Ca2+ Sc3+ Ti3+ VO2+ Cr2+ 5.5a Mn2+ Fe2+ 9.4 Co2+ 9.7 Ni2+ Cu2+ Zn2+ Ga3+ Ge
12.70 4.3 1.3 5.7 Cr3+ 3.66 10.6 Fe3+ 2.19 Co3+ 0.5b 9.9 7.5 9.0 2.6

Rb Sr Y3+ Zr4+ Nb Mo Tc Ru Rh3+ Pd2+ Ag+ Cd2+ In3+ Sn2+ Sb

13.18 7.7 –0.3 3.33c 1.0 12.0 10.1 3.9 3.4

Cs Ba2+ La3+ Hf Ta W Re Os Ir Pt Au Hg22+ 5.3d Tl+ Pb2+ Bi3+

13.36 8.5 Hg2+ 3.40 13.21 7.6 1.1

Ce3+ Pr3+ Nd3+ Pm Sm3+ Eu3+ Gd3+ Tb3+ Dy3+ Ho3+ Er3+ Tm3+ Yb3+ Lu3+
9.1b 9.4b 8.7b 8.6b 8.6d 9.1b 8.4d 8.4d 8.3 9.1b 8.2d 8.4b 8.2d

Ionic strength = 0 unless noted by superscript

a. Ionic strength = 1 M b. Ionic strength = 3 M c. Ionic strength = 2.5 M d. Ionic strength = 0.5 M
Ka
FIGURE 6-8 Acid dissociation constants (–log Ka) for aqueous metal ions: Mnⴙ ⴙ H2O Δ MOH(nⴚ1)ⴙ ⴙ Hⴙ .
For example, for Liⴙ, Ka = 10ⴚ13.64. In Chapter 8, we will learn that the numbers in this table are called pKa. Darkest
shades are strongest acids. [Data from R. M. Smith, A. E. Martell, and R. J. Motekaitis, NIST Critical Stability Constants of Metal
Complexes Database 46 (Gaithersburg, MD: National Institute of Standards and Technology, 2001).]

Amines are weak bases, and ammonium ions are weak acids. The “parent” of all
amines is ammonia, NH3. When a base such as methylamine reacts with water, the prod-
uct is the conjugate acid. That is, methylammonium ion produced in Reaction 6-27 is a
weak acid: Although we will usually write a base as B
 Ka and an acid as HA, it is important to realize
:

CH3NH3—Δ CH3NH2  Hⴙ———Ka  2.26 1011 (6-28)

that BHⴙ is also an acid and Aⴚ is also a

BH B base.

The methylammonium ion is the conjugate acid of methylamine. Methylammonium chloride is a weak acid
You should learn to recognize whether a compound is acidic or basic. The salt methylam- because
monium chloride, for example, dissociates in aqueous solution to give methylammonium 1. It dissociates into CH3NHⴙ ⴚ
3 and Cl .

cation and chloride: 2. CH3NHⴙ

3 is a weak acid, being conjugate to

 
CH3NH2, a weak base.
CH3NH3Cl (s) S CH3NH3 (aq)  Cl (aq) (6-29) 3. Clⴚ has no basic properties. It is conjugate
Methylammonium Methylammonium to HCl, a strong acid. That is, HCl dissociates
chloride ion completely.

Methylammonium ion, being the conjugate acid of methylamine, is a weak acid (Reaction
Challenge Phenol (C6H5OH) is a weak acid.
6-28). Chloride is the conjugate base of HCl, a strong acid. In other words, Cl has virtu- Explain why a solution of the ionic compound
ally no tendency to associate with H, or else HCl would not be a strong acid. potassium phenolate (C6H5OⴚKⴙ) is basic.
Methylammonium chloride is acidic because methylammonium ion is an acid and Cl is
not a base.
Metal cations, M n act as weak acids by acid hydrolysis to form M(OH)(n1).26 Figure 6-8
shows acid dissociation constants for the reaction
Ka
Mn  H2O Δ MOH(n1)  H Aqueous metal ions are associated with
(hydrated by) several H2O molecules, so a
Monovalent metal ions are very weak acids (Na, Ka  1013.9). Divalent ions tend to be more accurate way to write the acid
stronger (Fe2, Ka  109.4) and trivalent ions are stronger yet (Fe3, Ka  102.19). dissociation reaction is
M(H2O)nⴙ
x Δ M(H2O)xⴚ1(OH)
(nⴚ1)
ⴙ Hⴙ
Polyprotic Acids and Bases
Polyprotic acids and bases are compounds that can donate or accept more than one proton.
For example, oxalic acid is diprotic and phosphate is tribasic:
OO OO
™™ ™™
HOCCOH—T—Hⴙ  OCCOH— Ka1  5.37 102 (6-30)
Oxalic Monohydrogen
acid oxalate

6-7 Strengths of Acids and Bases 133

Notation for acid and base equilibrium OO OO
constants: Ka1 refers to the acidic species ™™ ™™
with the most protons and Kb1 refers to the 
OCCOH—T—H  OCCO— ⴙ 
Ka2  5.42 105 (6-31)
basic species with the least protons. The Oxalate
subscript “a” in acid dissociation constants will
usually be omitted. O O
™ ™
P –H2O—T— P –OH— Kb1  2.3 102

ç  
ç
O O O  OH (6-32)
O O
Phosphate Monohydrogen
phosphate

O O
™ ™
–H2O—T—
7
P P –OH— Kb2  1.60 10

ç 
ç (6-33)
O  OH O
O HO OH
Dihydrogen phosphate

O O
™ ™
P –H2O—T— P –OH Kb3  1.42 1012
O
ç ç
OH HO OH (6-34)
HO HO
Phosphoric
acid

Standard notation for successive acid dissociation constants of a polyprotic acid is K1, K2, K3,
and so on, with the subscript “a” usually omitted. We retain or omit the subscript as dictated
by clarity. For successive base hydrolysis constants, we retain the subscript “b.” The preced-
ing examples illustrate that Ka1 (or K1) refers to the acidic species with the most protons,
and Kb1 refers to the basic species with the least number of protons. Carbonic acid, a very
important diprotic carboxylic acid derived from CO2, is described in Box 6-4.

B OX 6 - 4 Carbonic Acid27
Carbonic acid is formed by the reaction of carbon dioxide with water: The reason for this anomaly is not that H2CO3 is unusual but,
rather, that the value commonly given for Ka1 applies to the equation
[CO2 (aq) ]
CO2 (g) Δ CO2 (aq) K  0.034 4 All dissolved CO2 Δ HCO
3  H

PCO2
( CO2 (aq)  H2CO3 )
O [HCO 
3 ] [H ]
关H2CO3兴 Ka1   4.46 107
CO2(aq)  H2O Δ C K ⬇ 0.002 [CO2 (aq)  H2CO3 ]
关CO2(aq)兴
HO OH Only about 0.2% of dissolved CO2 is in the form H2CO3. When the
Carbonic acid true value of [H2CO3] is used instead of the value [H2CO3 
H2CO3 Δ HCO3 

H Ka1  4.46 107 CO2(aq)], the value of the equilibrium constant becomes
Bicarbonate [HCO 
3 ] [H ]
Ka1  2 104
HCO
3 Δ CO2
3 H 
Ka2  4.69 10 11
[H2CO3 ]
Carbonate
The hydration of CO2 (reaction of CO2 with H2O) and dehydration
Its behavior as a diprotic acid appears anomalous at first, because of H2CO3 are slow reactions that can be demonstrated in a class-
the value of Ka1 is about 102 to 104 times smaller than Ka for other room.27 Living cells utilize the enzyme carbonic anhydrase to speed
carboxylic acids. the rate at which H2CO3 and CO2 equilibrate in order to process this
CH3CO2H HCO2H key metabolite. The enzyme provides an environment just right for the
Acetic acid Formic acid reaction of CO2 with OH, lowering the activation energy (the energy
Ka  1.75 105 Ka  1.80 104 barrier for the reaction) from 50 down to 26 kJ/mol and increasing the
N ‚ CCH2CO2H HOCH2CO2H rate of reaction by more than a factor of 106.
Cyanoacetic acid Glycolic acid Carbonic acid has limited stability in aqueous solution and is not
Ka  3.37 103 Ka  1.48 104 well characterized. The dimer (H2CO3)2 or oligomers (H2CO3)n
appear to exist in the solid state.28

134 CHAPTER 6 Chemical Equilibrium

Relation Between Ka and Kb
A most important relation exists between Ka and Kb of a conjugate acid-base pair in aqueous
solution. We can derive this result with the acid HA and its conjugate base A.
[H ][A ]
HA Δ H  A Ka 
[HA]
[HA][OH ]
A  H2O Δ HA  OH Kb 
[A ]
H2O Δ H  OH Kw  Ka ⴢ Kb
[H ][A ] [HA ][OH ]
 ⴢ
[HA ] [A ]
When the reactions are added, their equilibrium constants are multiplied to give
Relation between Ka and Kb
Ka ⴢ Kb  Kw (6-35) Ka ⴢ Kb ⴝ Kw for a conjugate acid-base pair in
for a conjugate pair:
aqueous solution.
Equation 6-35 applies to any acid and its conjugate base in aqueous solution.

EXAM PLE Finding Kb for the Conjugate Base

Ka for acetic acid is 1.75 105 (Reaction 6-26). Find Kb for acetate ion.

Solution This one is trivial:†

Kw 1.0 1014
Kb    5.7 1010
Ka 1.75 105
Test Yourself Ka for chloroacetic acid is 1.36 103. Find Kb for chloroacetate ion.
(Answer: 7.4 1012)

EXAM PLE Finding Ka for the Conjugate Acid

Kb for methylamine is 4.47 104 (Reaction 6-27). Find Ka for methylammonium ion.

Solution Once again,

Kw
Ka   2.2 1011
Kb
Test Yourself Kb for dimethylamine is 5.9 104. Find Ka for dimethylammonium
ion. (Answer: 1.7 1011)

For a diprotic acid, we can derive relationships between each of two acids and their
conjugate bases:
H2A Δ H  HA Ka1 HA Δ H  A2 Ka2
   
HA  H2O Δ H2A  OH Kb2 A 2
 H2O Δ HA  OH Kb1
   
H2O Δ H  OH Kw H 2O Δ H  OH Kw
The final results are
General relation
Ka1 ⴢ Kb2  Kw (6-36)
between Ka and Kb:

Ka2 ⴢ Kb1  Kw (6-37)

†
In this text, we use Kw  1014.00  1.0 1014 at 25C. The more accurate value from Table 6-1 is
Kw  1013.995. For acetic acid with Ka  104.756, the accurate value of Kb is 10(13.995 – 4.756)  109.239 
5.77 1010.

6-7 Strengths of Acids and Bases 135

 Challenge Derive the following results for a triprotic acid:

Ka1 ⴢ Kb3  Kw (6-38)

Ka2 ⴢ Kb2  Kw (6-39)

Ka3 ⴢ Kb1  Kw (6-40)

Shorthand for Organic Structures

We are beginning to encounter organic (carbon-containing) compounds in this book.
Chemists and biochemists use simple conventions for drawing molecules to avoid writing
every atom. Each vertex of a structure is understood to be a carbon atom, unless otherwise
labeled. In the shorthand, we usually omit bonds from carbon to hydrogen. Carbon forms four
chemical bonds. If you see carbon forming fewer than four bonds, the remaining bonds are
assumed to go to hydrogen atoms that are not written. Here is an example:

Dashed bond goes behind

the plane of the page. It is understood that there
HO H is a hydrogen attached to
this carbon.
H Wedge shows a bond
C C coming out of the plane
HO H
HO C OH of the page.
OH
C C HO

C C CH2 NH2 CH3 
NH2 CH3
Benzene, C6H6, has two equivalent resonance
structures, so all C—C bonds are equivalent. H H CH2 group
We often draw benzene rings with a circle in Epinephrine (also called adrenaline) Shorthand drawing of epinephrine
place of three double bonds.
The shorthand shows that the carbon atom at the top right of the six-membered benzene
ring forms three bonds to other carbon atoms (one single bond and one double bond), so there
must be a hydrogen atom attached to this carbon atom. The carbon atom at the left side of the
benzene ring forms three bonds to other carbon atoms and one bond to an oxygen atom. There
Benzene is no hidden hydrogen atom attached to this carbon. In the CH2 group adjacent to nitrogen,
C6H6 both hydrogen atoms are omitted in the shorthand structure.

Terms to Understand
acid Brønsted-Lowry base entropy overall formation constant
acid dissociation constant (Ka) carboxylate anion equilibrium constant pH
acidic solution carboxylic acid exothermic polyprotic acids
amine common ion effect Gibbs free energy polyprotic bases
ammonium ion complex ion hydronium ion protic solvent
aprotic solvent conjugate acid-base pair ion pair reaction quotient
autoprotolysis coprecipitation Le Châtelier’s principle salt
base cumulative formation constant Lewis acid saturated solution
base hydrolysis constant (Kb) disproportionation Lewis base solubility product
basic solution endothermic ligand standard state
Brønsted-Lowry acid enthalpy change neutralization stepwise formation constant

Summary
For the reaction aA  bB Δ c C  d D, the equilibrium constant is
K  [C]c[D]d/[A]a[B]b. Solute concentrations should be expressed
in moles per liter; gas concentrations should be in bars; and the
concentrations of pure solids, liquids, and solvents are omitted. If
the direction of a reaction is changed, K  1/K. If two reactions
are added, K3  K1K2. The equilibrium constant can be calculated
from the free-energy change for a chemical reaction: K  eG/RT.
The equation G  H  TS summarizes the observations that a
reaction is favored if it liberates heat (exothermic, negative H) or
increases disorder (positive S). Le Châtelier’s principle predicts
the effect on a chemical reaction when reactants or products are
added or temperature is changed. The reaction quotient, Q, tells how
a system must change to reach equilibrium.
The solubility product is the equilibrium constant for the disso-
lution of a solid salt into its constituent ions in aqueous solution. The
common ion effect is the observation that, if one of the ions of that

136 CHAPTER 6 Chemical Equilibrium

salt is already present in the solution, the solubility of a salt is de-
creased. Sometimes, we can selectively precipitate one ion from a
solution containing other ions by adding a suitable counterion. At
high concentration of ligand, a precipitated metal ion may redissolve
by forming soluble complex ions. In a metal-ion complex, the metal
is a Lewis acid (electron pair acceptor) and the ligand is a Lewis
base (electron pair donor).
Brønsted-Lowry acids are proton donors, and Brønsted-Lowry
bases are proton acceptors. An acid increases the concentration of
H3O in aqueous solution, and a base increases the concentration of
OH. An acid-base pair related through the gain or loss of a single
proton is described as conjugate. When a proton is transferred from
one molecule to another molecule of a protic solvent, the reaction is
called autoprotolysis.
The definition pH  –log[H] will be modified to include activ-
ity later. Ka is the equilibrium constant for the dissociation of an
acid: HA  H2O Δ H3O  A. The base hydrolysis constant
for the reaction B  H2O Δ BH  OH is Kb. When either Ka
or Kb is large, the acid or base is said to be strong; otherwise, the
acid or base is weak. Common strong acids and bases are listed in
Table 6-2, which you should memorize. The most common weak
acids are carboxylic acids (RCO2H), and the most common weak
bases are amines (R3N:). Carboxylate anions (RCO 2 ) are weak
bases, and ammonium ions (R3NH) are weak acids. Metal cations
are weak acids. For a conjugate acid-base pair in water, Ka ⴢKb  Kw.
For polyprotic acids, we denote successive acid dissociation con-
stants as Ka1, Ka2, Ka3, p , or just K1, K2, K3, p . For polybasic
species, we denote successive hydrolysis constants Kb1, Kb2, Kb3, p .
For a diprotic system, the relations between successive acid and base
equilibrium constants are Ka1 ⴢ Kb2  Kw and Ka2 ⴢ Kb1  Kw. For a
triprotic system, the relations are Ka1 ⴢKb3  Kw, Ka2 ⴢKb2  Kw, and
Ka3 ⴢ Kb1  Kw.
In the chemists’ shorthand for organic structures, each vertex is
a carbon atom. If fewer than four bonds to that carbon are shown, it is
understood that H atoms are attached to the carbon so that it makes
four bonds.

Exercises
6-A. Consider the following equilibria in aqueous solution: 6-C. Find [La3] in the solution when excess solid lanthanum
(1) Ag  Cl Δ AgCl(aq) K  2.0 103 iodate, La(IO3)3, is stirred with 0.050 M LiIO3 until the system
reaches equilibrium. Assume that IO3 from La(IO3)3 is negligible
(2) AgCl(aq)  Cl Δ AgCl K  9.3 101
2
compared with IO3 from LiIO3.
 
(3) AgCl(s) Δ Ag  Cl K  1.8 1010
6-D. Which will be more soluble (moles of metal dissolved per
(a) Calculate the numerical value of the equilibrium constant for the
liter of solution), Ba(IO3)2 (Ksp  1.5 109) or Ca(IO3)2 (Ksp 
reaction AgCl(s) Δ AgCl(aq).
7.1 107)? Give an example of a chemical reaction that might
(b) Calculate the concentration of AgCl(aq) in equilibrium with occur that would reverse the predicted solubilities.
excess undissolved solid AgCl.
(c) Find the numerical value of K for the reaction AgCl 6-E. Fe(III) precipitates from acidic solution by addition of OH to
2 Δ
AgCl(s)  Cl. form Fe(OH)3(s). At what concentration of OH will [Fe(III)] be
reduced to 1.0 1010 M? If Fe(II) is used instead, what concen-
6-B. Reaction 6-7 is allowed to come to equilibrium in a solution tration of OH will reduce [Fe(II)] to 1.0 1010 M?
initially containing 0.010 0 M BrO 3 , 0.010 0 M Cr
3
, and 1.00 M H.
To find the concentrations at equilibrium, we can construct a table 6-F. Is it possible to precipitate 99.0% of 0.010 M Ce3 by adding
showing initial and final concentrations (see below). We use the oxalate (C2O24 ) without precipitating 0.010 M Ca
2
?
stoichiometry coefficients of the reaction to say that if x mol of Br CaC2O4 Ksp  1.3 108
are created, then we must also make x mol of Cr2O2 7 and 8x mol of Ce2(C2O4 )3 Ksp  5.9 1030
H. To produce x mol of Br, we must have consumed x mol of
BrO 3 6-G. For a solution of Ni2 and ethylenediamine, the following
3 and 2x mol of Cr .
equilibrium constants apply at 20C:
(a) Write the equilibrium constant expression that you would use to
solve for x to find the concentrations at equilibrium. Do not try to Ni2  H2NCH2CH2NH2 Δ Ni(en)2 log K1  7.52
Ethylenediamine
solve the equation. (abbreviated en)
(b) Because K  1 1011, we suppose that the reaction will go Ni(en)2  en Δ Ni(en)2 log K2  6.32
2
nearly “to completion.” That is, we expect both the concentration of
Br and Cr2O72 to be close to 0.005 00 M at equilibrium. (Why?) Ni(en)2
2  en Δ Ni(en)2
3 log K3  4.49
That is, x ≈ 0.005 00 M. With this value of x, [H]  1.00  8x  Calculate the concentration of free Ni2 in a solution prepared by
1.04 M and [BrO 3 ]  0.010 0 – x  0.005 0 M. However, we can- mixing 0.100 mol of en plus 1.00 mL of 0.010 0 M Ni2 and diluting
not say [Cr3]  0.010 0 – 2x  0, because there must be some to 1.00 L with dilute base (which keeps all the en in its unprotonated
small concentration of Cr3 at equilibrium. Write [Cr3] for the form. Assume that nearly all nickel is in the form Ni(en)2 3 , so
concentration of Cr3and solve for [Cr3]. The limiting reagent in 3 ]  1.00
[Ni(en)2 105 M. Calculate the concentrations of
this example is Cr3. The reaction uses up Cr3 before consuming Ni(en)2 and Ni(en)22 to verify that they are negligible in compari-
BrO 3. son with Ni(en)2
3 .

BrO
3  2Cr3  4H2O Δ Br  Cr2O2
7  8H
Initial concentration 0.010 0 0.010 0 1.00
Final concentration 0.010 0 – x 0.010 0 – 2x x x 1.00  8x

Exercises 137
6-H. If each compound is dissolved in water, will the solution be 6-J. Histidine is a triprotic amino acid:
acidic, basic, or neutral? CO2H
CO2
(a) NaBr (e) (CH3)4NCl å NH
HC ® CH2 ® K1  3 10
2
å NH
(b) NaCH3CO (f) (CH3)4N 
CO2 N #£££££££4 HC ® CH2 ®
2
å H å N
(c) NH4 Cl (g) Fe(NO3)3 NH Hⴙ
 3 NH
 3
(d) K3PO4 1
K2  8.5 107 ¡
6-I. Succinic acid dissociates in two steps: ¡
CO2 @
CO2
O O O O å NH
å
HC ® CH2 ®
10 NH
™ ™ K1 ™ ™ K3  4.6 10
#£££££££4 HC ® CH2 ®
HOCCH2CH2COH——T——HOCCH2CH2CO  H  ⴙ
å N
N
K1  6.2 105 NH2 å
NH
 3
O O O O
™ ™ K2 ™ ™ What is the value of the equilibrium constant for the reaction
HOCCH2CH2CO——T——OCCH2CH2CO  Hⴙ CO2 CO2
K2  2.3 106 å NH å NH
HC ® CH2 ®  H2O T HC ® CH2 ®  OH
N Nⴙ
Calculate Kb1 and Kb2 for the following reactions: å å H
NH NH3
O O O O  3 
™ ™ Kb1 ™ ™
OCCH2CH2CO  H2O—T HOCCH2CH2CO  OH
 6-K. (a) From Kw in Table 6-1, calculate the pH of pure water at
0, 20, and 40C.
O O O O (b) For the reaction D2O Δ D  OD, K  [D][OD]  1.35
™ ™ Kb2 ™ ™ 1015 at 25C. In this equation, D stands for deuterium, which is the
HOCCH2CH2CO  H2O—T HOCCH2CH2COH  OH isotope 2H. What is the pD ( –log[D]) for neutral D2O?

Problems
Equilibrium and Thermodynamics 6-7. (a) A favorable entropy change occurs when S is positive.
6-1. To evaluate the equilibrium constant in Equation 6-2, we must Does the order of the system increase or decrease when S is positive?
express concentrations of solutes in mol/L, gases in bars, and omit (b) A favorable enthalpy change occurs when H is negative. Does
solids, liquids, and solvents. Explain why. the system absorb heat or give off heat when H is negative?
(c) Write the relation between G, H, and S. Use the results of
6-2. Why do we say that the equilibrium constant for the reaction
parts (a) and (b) to state whether G must be positive or negative
H2O Δ H  OH (or any other reaction) is dimensionless?
for a spontaneous change.
6-3. Explain the statement that predictions about the direction of a
6-8. For the reaction HCO 
3 Δ H  CO3 , G  59.0 kJ/mol
2
reaction based on Gibbs free energy or Le Châtelier’s principle are
at 298.15 K. Find the value of K for the reaction.
thermodynamic, not kinetic.
6-9. The formation of tetrafluoroethylene from its elements is
6-4. Write the expression for the equilibrium constant for each of
highly exothermic:
the following reactions. Write the pressure of a gaseous molecule,
X, as PX. 2F2(g)  2C(s) Δ F2C“CF2(g)

Fluorine Graphite Tetrafluoroethylene
(a) 3Ag (aq)  PO3
4 (aq) Δ Ag3PO4(s)
(b) C6H6(l)  152 O2(g) Δ 3H2O(l )  6CO2(g) (a) If a mixture of F2, graphite, and C2F4 is at equilibrium in a closed
container, will the reaction go to the right or to the left if F2 is added?
6-5. For the reaction 2A(g)  B(aq)  3C(l) Δ D(s)  3E(g), (b) Rare bacteria from the planet Teflon eat C2F4 and make Teflon
the concentrations at equilibrium are found to be for their cell walls. Will the reaction go to the right or to the left if
A: 2.8 103 Pa C: 12.8 M E: 3.6 104 Torr these bacteria are added?
2
B: 1.2 10 M D: 16.5 M F F F F
F
Find the numerical value of the equilibrium constant that would
F2 ç
C C C C
appear in a conventional table of equilibrium constants. ç çç çç ç F
C C C C Teflon
6-6. From the equations F F2
F F F F F
HOCl Δ H  OCl K  3.0 108
(c) Will the reaction go right or left if solid graphite is added?
HOCl  OBr Δ HOBr  OCl K  15
(Neglect any effect of increased pressure due to the decreased
find the value of K for the reaction HOBr Δ H  OBr. volume in the vessel when solid is added.)

138 CHAPTER 6 Chemical Equilibrium

(d) Will the reaction go right or left if the container is crushed to
one-eighth of its original volume?
(e) Does the equilibrium constant become larger or smaller if the
container is heated?
6-10. BaCl2 ⴢH2O(s) loses water when it is heated in an oven:
BaCl2 ⴢ H2O(s) Δ BaCl2(s)  H2O(g)
H  63.11 kJ/mol at 25C
S  148 J/(K ⴢ mol) at 25C
(a) Write the equilibrium constant for this reaction. Calculate the
vapor pressure of gaseous H2O (PH2O ) above BaCl2ⴢH2O at 298 K.
(b) If H and S are not temperature dependent (a poor assump-
tion), estimate the temperature at which PH2O above BaCl2 H2O(s)
will be 1 bar.
6-11. The equilibrium constant for the reaction of NH3(aq) 
H2O Δ NH4  OH is Kb  1.479 105 at 5C and 1.570 105
at 10C.
(a) Assuming H and S are constant in the interval 5–10C
(probably a good assumption for small T ), use Equation 6-8 to find
H  for the reaction in this temperature range.
(b) Describe how Equation 6-8 could be used to make a linear
graph to determine H, if H and S were constant over some
temperature range.
6-12. For H2(g)  Br2(g) Δ 2HBr(g), K  7.2 104 at 1 362 K
and H is positive. A vessel is charged with 48.0 Pa HBr, 1 370 Pa H2,
and 3 310 Pa Br2 at 1 362 K.
(a) Will the reaction proceed to the left or the right to reach
equilibrium?
(b) Calculate the pressure (in pascals) of each species in the vessel
at equilibrium.
(c) If the mixture at equilibrium is compressed to half of its original
volume, will the reaction proceed to the left or the right to reestablish
equilibrium?
(d) If the mixture at equilibrium is heated from 1 362 to 1 407 K, will
HBr be formed or consumed in order to reestablish equilibrium?
6-13. Henry’s law states that the concentration of a gas dissolved in
a liquid is proportional to the pressure of the gas. This law is a con-
sequence of the equilibrium
Kh [X]
X(g) Δ X(aq) Kh 
PX
6-16. Find [Cu2] in a solution saturated with Cu4(OH)6(SO4) if
[OH] is fixed at 1.0 106 M. Note that Cu4(OH)6(SO4) gives 1 mol
of SO42 for 4 mol of Cu2.
Cu4(OH)6(SO4 )(s) Δ 4Cu2  6OH  SO24
Ksp  2.3 1069
6-17. (a) From the solubility product of zinc ferrocyanide,
Zn2Fe(CN)6, calculate the concentration of Fe(CN)64 in 0.10 mM
ZnSO4 saturated with Zn2Fe(CN)6. Assume that Zn2Fe(CN)6 is a
negligible source of Zn2.
(b) What concentration of K4Fe(CN)6 should be in a suspension of
solid Zn2Fe(CN)6 in water to give [Zn2]  5.0 107 M?
6-18. Solubility products predict that cation A3 can be 99.999%
separated from cation B2 by precipitation with anion X. When the
separation is tried, we find 0.2% contamination of AX3(s) with B2.
Explain what might be happening.
6-19. A solution contains 0.050 0 M Ca2 and 0.030 0 M Ag. Can
99% of Ca2 be precipitated by sulfate without precipitating Ag?
What will be the concentration of Ca2 when Ag2SO4 begins to
precipitate?
6-20. A solution contains 0.010 M Ba2 and 0.010 M Ag. Can
99.90% of either ion be precipitated by chromate (CrO42) without
precipitating the other metal ion?
6-21. If a solution containing 0.10 M Cl, Br, I, and CrO 2
4 is
treated with Ag, in what order will the anions precipitate?
Complex Formation
6-22. Explain why the total solubility of lead in Figure 6-3 first de-
creases and then increases as [I] increases. Give an example of the
chemistry in each of the two domains.
6-23. Identify the Lewis acids in the following reactions:
ⴚ 
(a) BF3  NH3 Δ F3B ¬NH3
(b) F  AsF5 Δ AsF
6
6-24. The cumulative formation constant for SnCl2(aq) in 1.0 M
NaNO3 is 2  12. Find the concentration of SnCl2(aq) for a solu-
tion in which the concentrations of Sn2 and Cl are both somehow
fixed at 0.20 M.
6-25. Given the following equilibria, calculate the concentration of
each zinc species in a solution saturated with Zn(OH)2(s) and con-
taining [OH] at a fixed concentration of 3.2 107 M.

where Kh is called the Henry’s law constant. (The same law applies to Zn(OH) 2(s) Ksp  3 1016

other solvents, but the value of Kh is different for each solvent.) For the Zn(OH) 1 1 104
gasoline additive MTBE, Kh  1.71 M/bar. Suppose we have a closed Zn(OH)2(aq) 2 1010
2
container with aqueous solution and air in equilibrium. If the concen-
tration of MTBE in the water is 1.00 102 ppm ( 100 g MTBE/g Zn(OH)3 3 8 1013
solution ⬇ 100 g/mL), what is the pressure of MTBE in the air? Zn(OH)2
4 4 3 1015
CH3 ¬O¬C(CH3 )3 Methyl-t-butylether (MTBE, FM 88.15) 6-26. Although KOH, RbOH, and CsOH have little association
between metal and hydroxide in aqueous solution, Li and Na do
form complexes with OH:
Solubility Product
[LiOH(aq)]
6-14. Find the concentration of Cu in equilibrium with CuBr(s) Li  OH Δ LiOH(aq) K1   0.83
[Li ][OH ]
and 0.10 M Br.
Na  OH Δ NaOH(aq) K1  0.20
6-15. What concentration of Fe(CN)64 (ferrocyanide) is in equilib-
rium with 1.0 M Ag and Ag4Fe(CN)6(s). Express your answer Prepare a table like the one in Exercise 6-B showing initial and
with a prefix from Table 1-3. final concentrations of Na, OH, and NaOH(aq) in 1 F NaOH

Problems 139
solution. Calculate the fraction of sodium in the form NaOH(aq) Strengths of Acids and Bases
at equilibrium.
6-41. Make a list of the common strong acids and strong bases.
6-27. In Figure 6-3, the concentration of PbI2(aq) is independent of Memorize this list.
[I]. Use any of the equilibrium constants for Reactions 6-11 through
6-42. Write the formulas and names for three classes of weak acids
6-15 to find the equilibrium constant for the reaction PbI2(s) Δ
and two classes of weak bases.
PbI2(aq), which is equal to the concentration of PbI2(aq).
6-43. Write the Ka reaction for trichloroacetic acid, Cl3CCO2H, for
Acids and Bases 
anilinium ion, NH3 , and for lanthanum ion, La3.
6-28. Distinguish Lewis acids and bases from Brønsted-Lowry
acids and bases. Give an example of each. 6-44. Write the Kb reactions for pyridine and for sodium 2-mercap-
toethanol.
6-29. Fill in the blanks:
(a) The product of a reaction between a Lewis acid and a Lewis N⬊

⬊ ⬊

Na
⬊
HOCH2CH2S
base is called ________.
Pyridine Sodium 2-mercaptoethanol
(b) The bond between a Lewis acid and a Lewis base is called
________ or _______. 6-45. Write the Ka and Kb reactions of NaHCO3.
(c) Brønsted-Lowry acids and bases related by gain or loss of one
proton are said to be ________. 6-46. Write the stepwise acid-base reactions for the following ions
in water. Write the correct symbol (for example, Kb1) for the equi-
(d) A solution is acidic if _______. A solution is basic if _______.
librium constant for each reaction.
 
6-30. Why is the pH of distilled water usually 7? How can you (a) H3NCH2CH2NH3 (b) O O
prevent this from happening? Ethylenediammonium ion

6-31. Gaseous SO2 is created by combustion of sulfur-containing OCCH2CO
Malonate ion
fuels, especially coal. Explain how SO2 in the atmosphere makes
acidic rain. 6-47. Which is a stronger acid, (a) or (b)?
6-32. Use electron dot structures to show why tetramethylammonium (a) O (b) O
hydroxide, (CH3)4NOH, is an ionic compound. That is, show why
hydroxide is not covalently bound to the rest of the molecule. Cl2HCCOH ClH2CCOH
Dichloroacetic acid Chloroacetic acid
6-33. Identify the Brønsted-Lowry acids among the reactants in the
Ka = 8 102 Ka = 1.36 103
following reactions:
(a) KCN  HI Δ HCN  KI Which is a stronger base, (c) or (d)?
4  H2O Δ HPO4
(b) PO3 2
 OH (c) H2NNH2 (d) O
Hydrazine
6-34. Write the autoprotolysis reaction of H2SO4. Kb = 1.1 106 H2NCNH2
6-35. Identify the conjugate acid-base pairs in the following reac- Urea
tions: Kb = 1.5 1014
  
(a) H3NCH2CH2NH3  H2O Δ H3NCH2CH2NH2  H3O 6-48. Write the Kb reaction of CN. Given that the Ka value for
(b) HCN is 6.2 1010, calculate Kb for CN.
CO2H  N T CO2  NH
6-49. Write the Ka2 reaction of phosphoric acid (H3PO4) and the
Benzoic acid Pyridine Benzoate Pyridinium
Kb2 reaction of disodium oxalate (Na2C2O4).
pH 6-50. From the Kb values for phosphate in Equations 6-32 through

6-36. Calculate [H ] and pH for the following solutions: 6-34, calculate the three Ka values of phosphoric acid.
(a) 0.010 M HNO3 (d) 3.0 M HCl 6-51. From the following equilibrium constants, calculate the equi-
(b) 0.035 M KOH (e) 0.010 M [(CH3)4N]OH librium constant for the reaction HO2CCO2H Δ 2H  C2O2 4 .

(c) 0.030 M HCl Tetramethylammonium hydroxide

OO OO
6-37. Use Table 6-1 to calculate the pH of pure water at (a) 25C
and (b) 100C. HOCCOH T H   HOCCO  K 1 = 5.4 102
Oxalic acid
6-38. The equilibrium constant for the reaction H2O Δ H  OH
OO OO
is 1.0 1014 at 25C. What is the value of K for the reaction
4H2O Δ 4H  4OH? HOCCO T H  
OCCO K 2 5.4 105
Oxalate
6-39. An acidic solution containing 0.010 M La3 is treated with
NaOH until La(OH)3 precipitates. At what pH does this occur? 6-52. (a) Using only Ksp from Table 6-3, calculate how many
6-40. Use Le Châtelier’s principle and Kw in Table 6-1 to decide moles of Ca(OH)2 will dissolve in 1.00 L of water.
whether the autoprotolysis of water is endothermic or exothermic at (b) How will the solubility calculated in part (a) be affected by the
(a) 25C; (b) 100C; (c) 300C. K1 reaction in Table 6-3?

140 CHAPTER 6 Chemical Equilibrium

6-53. The planet Aragonose (which is made mostly of the mineral
aragonite, whose composition is CaCO3) has an atmosphere containing
methane and carbon dioxide, each at a pressure of 0.10 bar. The oceans
are saturated with aragonite and have a concentration of H equal to
1.8 107 M. Given the following equilibria, calculate how many
grams of calcium are contained in 2.00 L of Aragonose seawater.
CaCO3 (s, aragonite) Δ Ca2 (aq)  CO2
3 (aq) Ksp  6.0 109
CO2(g) Δ CO2(aq) KCO2  3.4 102
CO2(aq)  H2O(l) Δ HCO 
3 (aq)  H (aq) K1  4.5 107
HCO
3 (aq) Δ H(aq)  CO2
3 (aq) K2  4.7 1011
Don’t panic! Reverse the first reaction, add all the reactions together,
and see what cancels.

Problems 141