16.

11 APPLICATION OF THE SOLUBILITY PRODUCT PRINCIPLE TO QUALITATIVE ANALYSIS 683

Chemistry in Action Chemistry in Action Chemistry in Action Chemistry in Action Chemistry in Action Chemistry
Chemistry in Action Chemistry in Action Chemistry in Action Chemistry in Action Chemistry in Action Chemistry

How an Eggshell Is Formed

The formation of the shell of a hen’s egg is a fasci-

nating example of a natural precipitation process.
An average eggshell weighs about 5 grams and
is 40 percent calcium. Most of the calcium in an
eggshell is laid down within a 16 hour period. This
means that it is deposited at a rate of about 125 mil-
ligrams per hour. No hen can consume calcium fast
enough to meet this demand. Instead, it is supplied by
special bony masses in the hen’s long bones, which
accumulate large reserves of calcium for eggshell for-
mation. [The inorganic calcium component of the bone
is calcium phosphate, Ca3(PO4)2, an insoluble com-
pound.] If a hen is fed a low-calcium diet, her eggshells
become progressively thinner; she might have to mo-
bilize 10 percent of the total amount of calcium in her
bones just to lay one egg! When the food supply is
consistently low in calcium, egg production eventually
stops.
The eggshell is largely composed of calcite, a
crystalline form of calcium carbonate (CaCO3).
Normally, the raw materials, Ca2 and CO 2 3 , are
carried by the blood to the shell gland. The calcifica-
tion process is a precipitation reaction:
Ca2(aq)  CO23(aq) 34 CaCO3(s)
In the blood, free Ca2 ions are in equilibrium with
calcium ions bound to proteins. As the free ions are
taken up by the shell gland, more are provided by the
dissociation of the protein-bound calcium.
The carbonate ions necessary for eggshell for-
mation are a metabolic byproduct. Carbon dioxide
produced during metabolism is converted to carbonic
acid (H2CO3) by the enzyme carbonic anhydrase
(CA):
Chicken eggs.
X-ray micrograph of an eggshell,
showing columns of calcite.
CA
CO2(g)  H2O(l) 34 H2CO3(aq)
Carbonic acid ionizes stepwise to produce carbonate
ions:
H2CO3(aq) 34 H(aq)  HCO
3 (aq)
2
HCO 
3 (aq) 34 H (aq)  CO3 (aq)
Chickens do not perspire and so must pant to cool
themselves. Panting expels more CO2 from the
chicken’s body than normal respiration does.
According to Le Chatelier’s principle, panting will shift
the CO2–H2CO3 equilibrium shown above from right
to left, thereby lowering the concentration of the CO23
ions in solution and resulting in thin eggshells. One
remedy for this problem is to give chickens carbon-
ated water to drink in hot weather. The CO2 dissolved
in the water adds CO2 to the chicken’s body fluids
and shifts the CO2–H2CO3 equilibrium to the right.

KEY EQUATION [conjugate base]

• pH  pKa  log  (16.4) Henderson-Hasselbalch equation.
[acid]

SUMMARY OF FACTS 1. The common ion effect tends to suppress the ionization of a weak acid or a weak base.
AND CONCEPTS This action can be explained by Le Chatelier’s principle.
2. A buffer solution is a combination of either a weak acid and its weak conjugate base (sup-
plied by a salt) or a weak base and its weak conjugate acid (supplied by a salt); the solution
reacts with small amounts of added acid or base in such a way that the pH of the solution re-
mains nearly constant. Buffer systems play a vital role in maintaining the pH of body fluids.

Back Forward Main Menu TOC Study Guide TOC Textbook Website MHHE Website
 684 ACID-BASE EQUILIBRIA AND SOLUBILITY EQUILIBRIA

3. The pH at the equivalence point of an acid-base titration depends on hydrolysis of the salt
formed in the neutralization reaction. For strong acid–strong base titrations, the pH at the
equivalence point is 7; for weak acid–strong base titrations, the pH at the equivalence point
is greater than 7; for strong acid–weak base titrations, the pH at the equivalence point is
less than 7.
4. Acid-base indicators are weak organic acids or bases that change color at the equivalence
point in an acid-base neutralization reaction.
5. The solubility product Ksp expresses the equilibrium between a solid and its ions in solu-
tion. Solubility can be found from Ksp and vice versa.
6. The presence of a common ion decreases the solubility of a salt.
7. The solubility of slightly soluble salts containing basic anions increases as the hydrogen
ion concentration increases. The solubility of salts with anions derived from strong acids is
unaffected by pH.
8. Complex ions are formed in solution by the combination of a metal cation with a Lewis
base. The formation constant Kf measures the tendency toward the formation of a specific
complex ion. Complex ion formation can increase the solubility of an insoluble substance.
9. Qualitative analysis is the identification of cations and anions in solution.

KEY WORDS
Buffer solution, p. 649 End point, p. 661 Molar solubility, p. 666 Solubility, p. 666
Common ion effect, p. 646 Formation constant (Kf), p. 677 Qualitative analysis, p. 680 Solubility product (Ksp), p. 665
Complex ion, p. 676

QUESTIONS AND PROBLEMS†

THE COMMON ION EFFECT 16.6 Define pKa for a weak acid. What is the relation-
Review Questions ship between the value of the pKa and the strength
of the acid? Do the same for a weak base.
16.1 Use Le Chatelier’s principle to explain how the
16.7 The pKas of two monoprotic acids HA and HB are
common ion effect affects the pH of a solution.
5.9 and 8.1, respectively. Which of the two is the
16.2 Describe the effect on pH (increase, decrease, or no
stronger acid?
change) that results from each of the following ad-
16.8 Identify the buffer systems below:
ditions: (a) potassium acetate to an acetic acid so-
(a) KCl/HCl
lution; (b) ammonium nitrate to an ammonia solu-
(b) NH3/NH4NO3
tion; (c) sodium formate (HCOONa) to a formic acid
(c) Na2HPO4/NaH2PO4
(HCOOH) solution; (d) potassium chloride to a hy-
(d) KNO2/HNO2
drochloric acid solution; (e) barium iodide to a hy-
(e) KHSO4/H2SO4
droiodic acid solution.
(f ) HCOOK/HCOOH
Problems
Problems
16.3 Determine the pH of (a) a 0.40 M CH3COOH solu-
16.9 Calculate the pH of the buffer system made up of
tion, (b) a solution that is 0.40 M CH3COOH and
0.15 M NH3/0.35 M NH4Cl.
0.20 M CH3COONa.
16.10 Calculate the pH of the following two buffer solu-
16.4 Determine the pH of (a) a 0.20 M NH3 solution,
tions: (a) 2.0 M CH3COONa/2.0 M CH3COOH,
(b) a solution that is 0.20 M in NH3 and 0.30 M
(b) 0.20 M CH3COONa/0.20 M CH3COOH. Which
NH4Cl.
is the more effective buffer? Why?
16.11 The pH of a bicarbonate-carbonic acid buffer is 8.00.
BUFFER SOLUTIONS
Calculate the ratio of the concentration of carbonic
Review Questions acid (H2CO3) to that of the bicarbonate ion (HCO 3 ).
16.5 What is a buffer solution? What constitutes a buffer 16.12 What is the pH of the buffer 0.10 M Na2HPO4/
solution? 0.15 M KH2PO4?
†
The temperature is assumed to be 25°C for all the problems.

Back Forward Main Menu TOC Study Guide TOC Textbook Website MHHE Website

16.13 The pH of a sodium acetate–acetic acid buffer is
4.50. Calculate the ratio [CH3COO]/[CH3COOH].
16.14 The pH of blood plasma is 7.40. Assuming the prin-
cipal buffer system is HCO 3 /H2CO3, calculate the
ratio [HCO3 ]/[H 2 CO3 ]. Is this buffer more effective
against an added acid or an added base?
16.15 Calculate the pH of the 0.20 M NH3/0.20 M NH4Cl
buffer. What is the pH of the buffer after the addi-
tion of 10.0 mL of 0.10 M HCl to 65.0 mL of the
buffer?
16.16 Calculate the pH of 1.00 L of the buffer 1.00 M
CH3COONa/1.00 M CH3COOH before and after the
addition of (a) 0.080 mol NaOH, (b) 0.12 mol HCl.
(Assume that there is no change in volume.)
16.17 A diprotic acid, H2A, has the following ionization
constants: Ka1  1.1  103 and Ka2  2.5  106.
In order to make up a buffer solution of pH 5.80,
which combination would you choose? NaHA/H2A
or Na2A/NaHA.
16.18 A student is asked to prepare a buffer solution at
pH  8.60, using one of the following weak acids:
HA (Ka  2.7  103), HB (Ka  4.4  106), HC
(Ka  2.6  109). Which acid should she choose?
Why?
ACID-BASE TITRATIONS
Review Questions
16.19 Briefly describe what happens in an acid-base titra-
tion.
16.20 Sketch titration curves for the following acid-base
titrations: (a) HCl versus NaOH, (b) HCl versus
CH3NH2, (c) CH3COOH versus NaOH. In each
case, the base is added to the acid in an Erlenmeyer
flask. Your graphs should show pH on the y-axis and
volume of base added on the x-axis.
Problems
16.21 A 0.2688-g sample of a monoprotic acid neutralizes
16.4 mL of 0.08133 M KOH solution. Calculate the
molar mass of the acid.
16.22 A 5.00-g quantity of a diprotic acid was dissolved
in water and made up to exactly 250 mL. Calculate
the molar mass of the acid if 25.0 mL of this solu-
tion required 11.1 mL of 1.00 M KOH for neutral-
ization. Assume that both protons of the acid were
titrated.
16.23 In a titration experiment, 12.5 mL of 0.500 M H2SO4
neutralize 50.0 mL of NaOH. What is the concen-
tration of the NaOH solution?
16.24 In a titration experiment, 20.4 mL of 0.883 M HCOOH
neutralize 19.3 mL of Ba(OH)2. What is the con-
centration of the Ba(OH)2 solution?
16.25 A 0.1276-g sample of an unknown monoprotic acid
was dissolved in 25.0 mL of water and titrated with
Back Forward Main Menu TOC Study Guide TOC
QUESTIONS AND PROBLEMS 685
0.0633 M NaOH solution. The volume of base re-
quired to bring the solution to the equivalence point
was 18.4 mL. (a) Calculate the molar mass of the
acid. (b) After 10.0 mL of base had been added dur-
ing the titration, the pH was determined to be 5.87.
What is the Ka of the unknown acid?
16.26 A solution is made by mixing exactly 500 mL of
0.167 M NaOH with exactly 500 mL of 0.100 M
CH3COOH. Calculate the equilibrium concentra-
tions of H, CH3COOH, CH3COO, OH, and
Na.
16.27 Calculate the pH at the equivalence point for the fol-
lowing titration: 0.20 M HCl versus 0.20 M methyl-
amine.
16.28 Calculate the pH at the equivalence point for the fol-
lowing titration: 0.10 M HCOOH versus 0.10 M
NaOH.
ACID-BASE INDICATORS
Review Questions
16.29 Explain how an acid-base indicator works in a titra-
tion. What are the criteria for choosing an indicator
for a particular acid-base titration?
16.30 The amount of indicator used in an acid-base titra-
tion must be small. Why?
Problems
16.31 Referring to Table 16.1, specify which indicator or
indicators you would use for the following titrations:
(a) HCOOH versus NaOH, (b) HCl versus KOH, (c)
HNO3 versus CH3NH2.
16.32 A student carried out an acid-base titration by
adding NaOH solution from a buret to an
Erlenmeyer flask containing HCl solution and us-
ing phenolphthalein as indicator. At the equivalence
point, she observed a faint reddish-pink color.
However, after a few minutes, the solution gradu-
ally turned colorless. What do you suppose hap-
pened?
16.33 The ionization constant Ka of an indicator HIn is
1.0  106. The color of the nonionized form is red
and that of the ionized form is yellow. What is the
color of this indicator in a solution whose pH is
4.00?
16.34 The Ka of a certain indicator is 2.0  106. The
color of HIn is green and that of In is red. A few
drops of the indicator are added to a HCl solution,
which is then titrated against a NaOH solution. At
what pH will the indicator change color?
SOLUBILITY EQUILIBRIA
Review Questions
16.35 Use BaSO4 to distinguish between solubility, molar
Textbook Website MHHE Website
 686 ACID-BASE EQUILIBRIA AND SOLUBILITY EQUILIBRIA
solubility, and solubility product.
16.36 Why do we usually not quote the Ksp values for sol-
uble ionic compounds?
16.37 Write balanced equations and solubility product ex-
pressions for the solubility equilibria of the follow-
ing compounds: (a) CuBr, (b) ZnC2O4, (c) Ag2CrO4,
(d) Hg2Cl2, (e) AuCl3, (f) Mn3(PO4)2.
16.38 Write the solubility product expression for the ionic
compound AxBy.
16.39 How can we predict whether a precipitate will form
when two solutions are mixed?
16.40 Silver chloride has a larger Ksp than silver carbon-
ate (see Table 16.2). Does this mean that AgCl also
has a larger molar solubility than Ag2CO3?
Problems
16.41 Calculate the concentration of ions in the following
saturated solutions: (a) [I] in AgI solution with
[Ag]  9.1  109 M, (b) [Al3] in Al(OH)3 so-
lution with [OH]  2.9  109 M.
16.42 From the solubility data given, calculate the solu-
bility products for the following compounds: (a)
SrF2, 7.3  102 g/L, (b) Ag3PO4, 6.7  103 g/L.
16.43 The molar solubility of MnCO3 is 4.2  106 M.
What is Ksp for this compound?
16.44 The solubility of an ionic compound MX (molar
mass  346 g) is 4.63  103 g/L. What is Ksp for
the compound?
16.45 The solubility of an ionic compound M2X3 (molar
mass  288 g) is 3.6  1017 g/L. What is Ksp for
the compound?
16.46 Using data from Table 16.2, calculate the molar sol-
ubility of CaF2.
16.47 What is the pH of a saturated zinc hydroxide solu-
tion?
16.48 The pH of a saturated solution of a metal hydrox-
ide MOH is 9.68. Calculate the Ksp for the com-
pound.
16.49 If 20.0 mL of 0.10 M Ba(NO3)2 are added to 50.0
mL of 0.10 M Na2CO3, will BaCO3 precipitate?
16.50 A volume of 75 mL of 0.060 M NaF is mixed with
25 mL of 0.15 M Sr(NO3)2. Calculate the concen-
trations in the final solution of NO  2
3 , Na , Sr , and
 10
F . (Ksp for SrF2  2.0  10 .)
FRACTIONAL PRECIPITATION
Problems
16.51 Solid NaI is slowly added to a solution that is
0.010 M in Cu and 0.010 M in Ag. (a) Which
compound will begin to precipitate first? (b) Cal-
culate [Ag] when CuI just begins to precipitate. (c)
What percent of Ag remains in solution at this
point?
Back Forward Main Menu TOC Study Guide TOC
16.52 Find the approximate pH range suitable for the
separation of Fe3 and Zn2 by precipitation of
Fe(OH)3 from a solution that is initially 0.010 M in
both Fe3 and Zn2.
THE COMMON ION EFFECT AND SOLUBILITY
Review Questions
16.53 How does the common ion effect influence solubil-
ity equilibria? Use Le Chatelier’s principle to ex-
plain the decrease in solubility of CaCO3 in a
Na2CO3 solution.
16.54 The molar solubility of AgCl in 6.5  103 M
AgNO3 is 2.5  108 M. In deriving Ksp from these
data, which of the following assumptions are rea-
sonable?
(a) Ksp is the same as solubility.
(b) Ksp of AgCl is the same in 6.5  103 M AgNO3
as in pure water.
(c) Solubility of AgCl is independent of the con-
centration of AgNO3.
(d) [Ag] in solution does not change significantly
upon the addition of AgCl to 6.5  103 M
AgNO3.
(e) [Ag] in solution after the addition of AgCl to
6.5  103 M AgNO3 is the same as it would
be in pure water.
Problems
16.55 How many grams of CaCO3 will dissolve in 3.0 
102 mL of 0.050 M Ca(NO3)2?
16.56 The solubility product of PbBr2 is 8.9  106.
Determine the molar solubility (a) in pure water,
(b) in 0.20 M KBr solution, (c) in 0.20 M Pb(NO3)2
solution.
16.57 Calculate the molar solubility of AgCl in a solution
made by dissolving 10.0 g of CaCl2 in 1.00 L of
solution.
16.58 Calculate the molar solubility of BaSO4 (a) in wa-
ter, (b) in a solution containing 1.0 M SO24 ions.
pH AND SOLUBILITY
Problems
16.59 Which of the following ionic compounds will be
more soluble in acid solution than in water?
(a) BaSO4, (b) PbCl2, (c) Fe(OH)3, (d) CaCO3
16.60 Which of the following will be more soluble in acid
solution than in pure water? (a) CuI, (b) Ag2SO4,
(c) Zn(OH)2, (d) BaC2O4, (e) Ca3(PO4)2
16.61 Compare the molar solubility of Mg(OH)2 in water
and in a solution buffered at a pH of 9.0.
16.62 Calculate the molar solubility of Fe(OH)2 at (a) pH
8.00, (b) pH 10.00.
16.63 The solubility product of Mg(OH)2 is 1.2  1011.
Textbook Website MHHE Website

What minimum OH concentration must be attained
(for example, by adding NaOH) to decrease the
Mg2 concentration in a solution of Mg(NO3)2 to
less than 1.0  1010 M?
16.64 Calculate whether or not a precipitate will form if
2.00 mL of 0.60 M NH3 are added to 1.0 L of 1.0 
103 M FeSO4.
COMPLEX ION EQUILIBRIA AND SOLUBILITY
Review Questions
1. Calculate the range of the ratio [conjugate
16.65 Explain the formation of complexes in Table 16.3
in terms of Lewis acid-base theory.
16.66 Give an example to illustrate the general effect of
complex ion formation on solubility.
Problems
16.67 If 2.50 g of CuSO4 are dissolved in 9.0  102 mL
of 0.30 M NH3, what are the concentrations of Cu2,
Cu(NH3)2 4 , and NH3 at equilibrium?
16.68 Calculate the concentrations of Cd2, Cd(CN)2 4 ,
and CN at equilibrium when 0.50 g of Cd(NO3)2
dissolves in 5.0  102 mL of 0.50 M NaCN.
16.69 If NaOH is added to 0.010 M Al3, which will be
the predominant species at equilibrium: Al(OH)3 or
Al(OH) 4 ? The pH of the solution is 14.00. [Kf for
Al(OH) 4  2.0  10 .]
33
16.70 Calculate the molar solubility of AgI in a 1.0 M NH3
solution.
16.71 Both Ag and Zn2 form complex ions with NH3.
Write balanced equations for the reactions.
However, Zn(OH)2 is soluble in 6 M NaOH, and
AgOH is not. Explain.
16.72 Explain, with balanced ionic equations, why (a)
CuI2 dissolves in ammonia solution, (b) AgBr dis-
solves in NaCN solution, (c) HgCl2 dissolves in KCl
solution.
QUALITATIVE ANALYSIS
Review Questions
16.73 Outline the general procedure of qualitative analy-
sis.
16.74 Give two examples of metal ions in each group (1
through 5) in the qualitative analysis scheme.
Problems
16.75 In a group 1 analysis, a student obtained a precipi-
tate containing both AgCl and PbCl2. Suggest one
reagent that would allow her to separate AgCl(s)
from PbCl2(s).
16.76 In a group 1 analysis, a student adds HCl acid to the
unknown solution to make [Cl]  0.15 M. Some
PbCl2 precipitates. Calculate the concentration of
Back Forward Main Menu TOC Study Guide TOC
QUESTIONS AND PROBLEMS 687
Pb2 remaining in solution.
16.77 Both KCl and NH4Cl are white solids. Suggest one
reagent that would allow you to distinguish between
these two compounds.
16.78 Describe a simple test that would allow you to dis-
tinguish between AgNO3(s) and Cu(NO3)2(s).
ADDITIONAL PROBLEMS
16.79 The buffer range is defined by the equation pH 
pKa
base]/[acid] that corresponds to this equation.
16.80 The pKa of the indicator methyl orange is 3.46. Over
what pH range does this indicator change from 90
percent HIn to 90 percent In?
16.81 Sketch the titration curve of a weak acid versus a
strong base like the one shown in Figure 16.4. On
your graph indicate the volume of base used at the
equivalence point and also at the half-equivalence
point, that is, the point at which half of the acid has
been neutralized. Show how you can measure the
pH of the solution at the half-equivalence point.
Using Equation (16.4), explain how you can deter-
mine the pKa of the acid by this procedure.
16.82 A 200-mL volume of NaOH solution was added to
400 mL of a 2.00 M HNO2 solution. The pH of the
mixed solution was 1.50 units greater than that of
the original acid solution. Calculate the molarity of
the NaOH solution.
16.83 The pKa of butyric acid (HBut) is 4.7. Calculate Kb
for the butyrate ion (But).
16.84 A solution is made by mixing exactly 500 mL of
0.167 M NaOH with exactly 500 mL 0.100 M
CH3COOH. Calculate the equilibrium concentra-
tions of H, CH3COOH, CH3COO, OH, and
Na.
16.85 Cd(OH)2 is an insoluble compound. It dissolves in
excess NaOH in solution. Write a balanced ionic
equation for this reaction. What type of reaction is
this?
16.86 A student mixes 50.0 mL of 1.00 M Ba(OH)2 with
86.4 mL of 0.494 M H2SO4. Calculate the mass of
BaSO4 formed and the pH of the mixed solution.
16.87 For which of the following reactions is the equilib-
rium constant called a solubility product?
(a) Zn(OH)2(s)  2OH(aq) 34 Zn(OH)2 4 (aq)
(b) 3Ca2(aq)  2PO3 4 (aq) 34 Ca 3 (PO 4 2(s)
)
(c) CaCO3(s)  2H(aq) 34
Ca2(aq)  H2O(l)  CO2(g)
(d) PbI2(s) 34 Pb2(aq)  2I(aq)
16.88 A 2.0-L kettle contains 116 g of boiler scale
(CaCO3). How many times would the kettle have to
be completely filled with distilled water to remove
all of the deposit at 25°C?
16.89 Equal volumes of 0.12 M AgNO3 and 0.14 M ZnCl2
Textbook Website MHHE Website
 688 ACID-BASE EQUILIBRIA AND SOLUBILITY EQUILIBRIA
solution are mixed. Calculate the equilibrium con-
centrations of Ag, Cl, Zn2, and NO 3.
16.90 Calculate the solubility (in g/L) of Ag2CO3.
16.91 Find the approximate pH range suitable for sepa-
rating Fe3 and Zn2 by the precipitation of
Fe(OH)3 from a solution that is initially 0.010 M in
Fe3 and Zn2.
16.92 A volume of 25.0 mL of 0.100 M HCl is titrated
against a 0.100 M CH3NH2 solution added to it from
a buret. Calculate the pH values of the solution (a)
after 10.0 mL of CH3NH2 solution have been added,
(b) after 25.0 mL of CH3NH2 solution have been
added, (c) after 35.0 mL of CH3NH2 solution have
been added.
16.93 The molar solubility of Pb(IO3)2 in a 0.10 M NaIO3
solution is 2.4  1011 mol/L. What is Ksp for
Pb(IO3)2?
16.94 When a KI solution was added to a solution of mer-
cury(II) chloride, a precipitate [mercury(II) iodide]
formed. A student plotted the mass of the precipi-
tate versus the volume of the KI solution added and
obtained the following graph. Explain the appear-
ance of the graph.
Mass of HgI2 formed
Volume of KI added
16.95 Barium is a toxic substance that can seriously im-
pair heart function. For an X ray of the gastroin-
testinal tract, a patient drinks an aqueous suspension
of 20 g BaSO4. If this substance were to equilibrate
with the 5.0 L of the blood in the patient’s body,
what would be [Ba2]? For a good estimate, we may
assume that the temperature is at 25°C. Why is
Ba(NO3)2 not chosen for this procedure?
16.96 The pKa of phenolphthalein is 9.10. Over what pH
range does this indicator change from 95 percent
HIn to 95 percent In?
16.97 Solid NaI is slowly added to a solution that is
0.010 M in Cu and 0.010 M in Ag. (a) Which com-
pound will begin to precipitate first? (b) Calculate
[Ag] when CuI just begins to precipitate. (c) What
percent of Ag remains in solution at this point?
16.98 Cacodylic acid is (CH3)2AsO2H. Its ionization con-
stant is 6.4  107. (a) Calculate the pH of 50.0 mL
of a 0.10 M solution of the acid. (b) Calculate the
pH of 25.0 mL of 0.15 M (CH3)2AsO2Na. (c) Mix
Back Forward Main Menu TOC
the solutions in part (a) and part (b). Calculate the
pH of the resulting solution.
16.99 Radiochemical techniques are useful in estimating
the solubility product of many compounds. In one
experiment, 50.0 mL of a 0.010 M AgNO3 solution
containing a silver isotope with a radioactivity of
74,025 counts per min per mL were mixed with
100 mL of a 0.030 M NaIO3 solution. The mixed
solution was diluted to 500 mL and filtered to re-
move all of the AgIO3 precipitate. The remaining
solution was found to have a radioactivity of 44.4
counts per min per mL. What is the Ksp of AgIO3?
16.100 The molar mass of a certain metal carbonate, MCO3,
can be determined by adding an excess of HCl acid
to react with all the carbonate and then “back-titrat-
ing” the remaining acid with NaOH. (a) Write an
equation for these reactions. (b) In a certain exper-
iment, 20.00 mL of 0.0800 M HCl were added to a
0.1022-g sample of MCO3. The excess HCl required
5.64 mL of 0.1000 M NaOH for neutralization.
Calculate the molar mass of the carbonate and iden-
tify M.
16.101 Acid-base reactions usually go to completion.
Confirm this statement by calculating the equilib-
rium constant for each of the following cases: (a) A
strong acid reacting with a strong base. (b) A strong
acid reacting with a weak base (NH3). (c) A weak
acid (CH3COOH) reacting with a strong base. (d) A
weak acid (CH3COOH) reacting with a weak base
(NH3). (Hint: Strong acids exist as H ions and
strong bases exist as OH ions in solution. You need
to look up Ka, Kb, and Kw.)
16.102 Calculate x, the number of molecules of water in ox-
alic acid hydrate, H2C2O4  xH2O, from the follow-
ing data: 5.00 g of the compound is made up to ex-
actly 250 mL solution, and 25.0 mL of this solution
requires 15.9 mL of 0.500 M NaOH solution for neu-
tralization.
16.103 Describe how you would prepare a 1-L 0.20 M
CH3COONa/0.20 M CH3COOH buffer system by
(a) mixing a solution of CH3COOH with a solution
of CH3COONa, (b) reacting a solution of
CH3COOH with a solution of NaOH, and (c) react-
ing a solution of CH3COONa with a solution of HCl.
16.104 Phenolphthalein is the common indicator for the
titration of a strong acid with a strong base. (a) If
the pKa of phenolphthalein is 9.10, what is the ra-
tio of the nonionized form of the indicator (color-
less) to the ionized form (reddish pink) at pH 8.00?
(b) If 2 drops of 0.060 M phenolphthalein are used
in a titration involving a 50.0-mL volume, what is
the concentration of the ionized form at pH 8.00?
(Assume that 1 drop  0.050 mL.)
Study Guide TOC Textbook Website MHHE Website

16.105 Oil paintings containing lead(II) compounds as con-
stituents of their pigments darken over the years.
Suggest a chemical reason for the color change.
16.106 What reagents would you employ to separate the
following pairs of ions in solution? (a) Na and
Ba2, (b) K and Pb2, (c) Zn2 and Hg2.
16.107 Look up the Ksp values for BaSO4 and SrSO4 in
Table 16.2. Calculate the concentrations of Ba2,
Sr2, and SO2 4 in a solution that is saturated with
both compounds.
16.108 In principle, amphoteric oxides, such as Al2O3 and
BeO can be used to prepare buffer solutions because
they possess both acidic and basic properties (see
Section 15.11). Explain why these compounds are
of little practical use as buffer components.
16.109 CaSO4 (Ksp  2.4  105) has a larger Ksp value
than that of Ag2SO4 (Ksp  1.4  105). Does it
follow that CaSO4 also has greater solubility (g/L)?
16.110 When lemon juice is squirted into tea, the color be-
comes lighter. In part, the color change is due to di-
lution, but the main reason for the change is an acid-
base reaction. What is the reaction? (Hint: Tea
contains “polyphenols” which are weak acids and
lemon juice contains citric acid.)
16.111 How many milliliters of 1.0 M NaOH must be added
to a 200 mL of 0.10 M NaH2PO4 to make a buffer
solution with a pH of 7.50?
16.112 The maximum allowable concentration of Pb2 ions
in drinking water is 0.05 ppm (that is, 0.05 g of Pb2
in one million grams of water). Is this guideline ex-
ceeded if an underground water supply is at equi-
librium with the mineral anglesite, PbSO4 (Ksp 
1.6  108)?
16.113 One of the most common antibiotics is penicillin G
(benzylpenicillinic acid), which has the following
structure:
O which ion (Ca2 or Mg2) would you remove first?
B
H COOH
O Answers to Practice Exercises: 16.1 4.01. 16.2 (a) and
H3C C J
G NOC H
C A A
D C OCO NOCO CH2
H3C S A B a 1-L solution. 16.5 (a) 2.19, (b) 3.95, (c) 8.02, (d) 11.39.
H H O 16.6 5.92. 16.7 (a) Bromophenol blue, methyl orange, methyl
It is a weak monoprotic acid:
HP 34 H  P Ka  1.64  103
where HP denotes the parent acid and P the con-
jugate base. Penicillin G is produced by growing
molds in fermentation tanks at 25°C and a pH range
of 4.5 to 5.0. The crude form of this antibiotic is ob-
tained by extracting the fermentation broth with an
Back Forward Main Menu TOC Study Guide TOC
QUESTIONS AND PROBLEMS 689
organic solvent in which the acid is soluble. (a)
Identify the acidic hydrogen atom. (b) In one stage
of purification, the organic extract of the crude peni-
cillin G is treated with a buffer solution at pH 
6.50. What is the ratio of the conjugate base of peni-
cillin G to the acid at this pH? Would you expect
the conjugate base to be more soluble in water than
the acid? (c) Penicillin G is not suitable for oral ad-
ministration, but the sodium salt (NaP) is because it
is soluble. Calculate the pH of a 0.12 M NaP solu-
tion formed when a tablet containing the salt is dis-
solved in a glass of water.
16.114 Which of the following solutions has the highest
[H]? (a) 0.10 M HF, (b) 0.10 M HF in 0.10 M NaF,
(c) 0.10 M HF in 0.10 M SbF5. (Hint: SbF5 reacts
with F  to form the complex ion SbF 6 .)
16.115 Distribution curves show how the fractions of non-
ionized acid and its conjugate base vary as a func-
tion of pH of the medium. Plot distribution curves
for CH3COOH and its conjugate base CH3COO in
solution. Your graph should show fraction as the y
axis and pH as the x axis. What are the fractions and
pH at the point where these two curves intersect?
16.116 Water containing Ca2 and Mg2 ions is called
hard water and is unsuitable for some household
and industrial use because these ions react with soap
to form insoluble salts, or curds. One way to re-
move the Ca2 ions from hard water is by adding
washing soda (Na2CO3  10H2O). (a) The molar
solubility of CaCO3 is 9.3  105 M. What is its
molar solubility in a 0.050 M Na2CO3 solution? (b)
Why are Mg2 ions not removed by this procedure?
(c) The Mg2 ions are removed as Mg(OH)2 by
adding slaked lime [Ca(OH)2] to the water to pro-
duce a saturated solution. Calculate the pH of a sat-
urated Ca(OH)2 solution. (d) What is the concen-
tration of Mg2 ions at this pH? (e) In general,
Why?
(c). 16.3 9.17; 9.20. 16.4 Weigh out Na2CO3 and NaHCO3 in
mole ratio of 0.60 to 1.0. Dissolve in enough water to make up
red, and chlorophenol blue; (b) all except thymol blue, bro-
mophenol blue, and methyl orange; (c) cresol red and phe-
nolphthalein. 16.8 2.0  1014. 16.9 1.9  103 g/L. 16.10 No.
16.11 (a) 1.6  109 M, (b) 2.6  106 M. 16.12 (a)
1.7  104 g/L, (b) 1.4  107 g/L. 16.13 (a) More soluble in
acid solution, (b) more soluble in acid solution, (c) about the
same. 16.14 A precipitate of Fe(OH)2 will form. 16.15 [Cu2] 
1.2  1013 M, [Cu(NH3)2 4 ]  0.017 M, [NH3]  0.23 M.
16.16 3.5  103 mol/L.
Textbook Website MHHE Website