Chemprincch8 8e

CHAPTER 8
APPLICATIONS OF AQUEOUS EQUILIBRIA
Buffers
15. A buffer solution is one that resists a change in its pH when either hydroxide ions or protons
(H+) are added. Any solution that contains a weak acid and its conjugate base or a weak base
and its conjugate acid is classified as a buffer. The pH of a buffer depends on the [base]/[acid]
ratio. When H+ is added to a buffer, the weak base component of the buffer reacts with the H+
and forms the acid component of the buffer. Even though the concentrations of the acid and
base components of the buffer change some, the ratio of [base]/[acid] does not change that
much. This translates into a pH that doesn’t change much. When OH− is added to a buffer, the
weak acid component is converted into the base com-ponent of the buffer. Again, the
[base]/[acid] ratio does not change a lot (unless a large quantity of OH− is added), so the pH
does not change much.
H+(aq) + CO32−(aq) → HCO3−(aq); OH−(aq) + HCO3−(aq) → H2O(l) + CO32−(aq)
16. When [HA] = [A−] (or [BH+] = [B]) for a buffer, the pH of the solution is equal to the pKa value
for the acid component of the buffer (pH = pKa because [H+] = Ka). A best buffer has equal
concentrations of the acid and base components so it is equally efficient at absorbing H+ and
OH−. For a pH = 4.00 buffer, we would choose the acid component having a Ka close to 10 −4.00
= 1.0 × 10 −4 (pH = pKa for a best buffer). For a pH = 10.00 buffer, we would want the acid
component of the buffer to have a Ka close to 10 −10.00 = 1.0 × 10 −10 . Of course, we can have a
buffer solution made from a weak base and its conjugate acid. For a pH = 10.00 buffer, our
conjugate acid should have Ka ≈ 1.0 × 10 −10 , which translates into a Kb value of the base close
to 1.0 × 10 −4 (Kb = Kw/Ka for conjugate acid-base pairs).
The capacity of a buffer is a measure of how much strong acid or strong base the buffer can
neutralize. All the buffers listed have the same pH (= pKa = 4.74) because they all have a 1 : 1
concentration ratio between the weak acid and the conjugate base. The 1.0 M buffer has the
greatest capacity; the 0.01 M buffer the least capacity. In general, the larger the concen-trations
of weak acid and conjugate base, the greater is the buffer capacity, that is, the more strong acid
or strong base that can be neutralized with little pH change.
17. Only the third beaker represents a buffer solution. A weak acid and its conjugate base must
both be present in large quantities in order to have a buffer solution. This is only the case in
the third beaker. The first beaker respresents a beaker full of strong acid which is 100°%
dissociated. The second beaker represents a weak acid solution. In a weak acid solution, only
a small fraction of the acid is dissociated. In this representation, 1/10 of the weak acid has
dissociated. The only B− present in this beaker is from the dissociation of the weak acid. A
buffer solution has B− added from another source.
273
274 CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA
18. A buffer solution is a solution containing a weak acid plus its conjugate base or a weak base
plus its conjugate acid. Solution c contains a weak acid (HOCl) plus its conjugate base (OCl−),
so it is a buffer. Solution e is also a buffer solution. It contains a weak base (H2NNH2) plus its
conjugate acid (H2NNH3+).
Solution a contains a strong acid (HBr) and a weak acid (HOBr). Solution b contains a strong
acid (HClO4) and a strong base (RbOH). Solution d contains a strong base (KOH) and a weak
base (HONH2).
[base] [base]  [base] 

19. pH = pKa + log ; when [acid] > [base], then < 1 and log   < 0.
[acid] [acid]  [acid] 
From the Henderson-Hasselbalch equation, if the log term is negative, then pH < pKa. When
one has more acid than base in a buffer, the pH will be on the acidic side of the pKa value; that
is, the pH is at a value lower than the pKa value. When one has more base than acid in a buffer
([conjugate base] > [weak acid]), then the log term in the Henderson-Hasselbalch equation is
positive, resulting in pH > pKa. When one has more base than acid in a buffer, the pH is on the
basic side of the pKa value; that is, the pH is at a value greater than the pKa value. The other
scenario you can run across in a buffer is when [acid] = [base]. Here, the log term is equal to
zero, and pH = pKa.
+
[ NH 4 ][OH − ]
20. NH3 + H2O ⇌ NH4 + OH + −
Kb = ; taking the −log of the Kb expression:
[ NH 3 ]
+ +
[ NH 4 ] [ NH 4 ]
−log Kb = −log[OH−] − log , −log[OH−] = −log Kb + log
[ NH 3 ] [ NH 3 ]
+
[ NH 4 ] [acid]
pOH = pKb + log or pOH = pKb + log
[ NH 3 ] [base]
21. a. This is a weak acid problem. Let HC3H5O2 = HOPr and C3H5O2− = OPr−.
HOPr(aq) ⇌ H+(aq) + OPr−(aq) Ka = 1.3 × 10−5

Initial 0.100 M ~0 0
x mol/L HOPr dissociates to reach equilibrium
Change −x → +x +x
Equil. 0.100 − x x x
[H + ][OPr − ] x2 x2
Ka = 1.3 × 10−5 = = ≈
[HOPr] 0.100 − x 0.100
x = [H+] = 1.1 × 10−3 M; pH = 2.96; assumptions good by the 5% rule.
b. This is a weak base problem.

CHAPTER 8 APPLICATIONS OF AQUEOUS EQUILIBRIA 275
⇌
Kw
OPr−(aq) + H2O(l) HOPr(aq) + OH−(aq) Kb = = 7.7 × 10−10
Ka
Initial 0.100 M 0 ~0
x mol/L OPr− reacts with H2O to reach equilibrium
[HOPr][OH − ] x2 x2
Kb = 7.7 × 10−10 = = ≈
[OPr − ] 0.100 − x 0.100
x = [OH−] = 8.8 × 10−6 M; pOH = 5.06; pH = 8.94; assumptions good.
c. Pure H2O, [H+] = [OH−] = 1.0 × 10−7 M; pH = 7.00
d. This solution contains a weak acid and its conjugate base. This is a buffer solution. We
will solve for the pH through the weak acid equilibrium reaction.
HOPr(aq) ⇌ H+(aq) + OPr−(aq) Ka = 1.3 × 10−5

Initial 0.100 M ~0 0.100 M
Equil. 0.100 − x x 0.100 + x
(0.100 + x)( x) (0.100)( x)
1.3 × 10−5 = ≈ = x = [H+]
0.100 − x 0.100
[H+] = 1.3 × 10−5 M; pH = 4.89; assumptions good.
Alternately, we can use the Henderson-Hasselbalch equation to calculate the pH of buffer

solutions.
[base]  0.100 
pH = pKa + log = pKa + log   = pKa = −log(1.3 × 10−5) = 4.89
[acid]  0.100 
The Henderson-Hasselbalch equation will be valid when an assumption of the type 0.1 + x
≈ 0.1 that we just made in this problem is valid. From a practical standpoint, this will
almost always be true for useful buffer solutions. If the assumption is not valid, the solution
will have such a low buffering capacity it will not be of any use to control the pH. Note:
The Henderson-Hasselbalch equation can only be used to solve for the pH of buffer
solutions.
22. a. We have a weak acid (HOPr = HC3H5O2) and a strong acid (HCl) present. The amount of
H+ donated by the weak acid will be negligible. To prove it lets consider the weak acid
equilibrium reaction:
HOPr ⇌ H+ + OPr− Ka = 1.3 × 10−5

Initial 0.100 M 0.020 M 0
Equil. 0.100 − x 0.020 + x x
[H+] = 0.020 + x ≈ 0.020 M; pH = 1.70; assumption good (x = 6.5 × 10−5 is << 0.020).
Note: The H+ contribution from the weak acid HOPr was negligible. The pH of the
solution can be determined by only considering the amount of strong acid present.
b. Added H+ reacts completely with the best base present, OPr−.
OPr− + H+ → HOPr
Before 0.100 M 0.020 M 0
Change −0.020 −0.020 → +0.020 Reacts completely
After 0.080 0 0.020 M
After reaction, a weak acid, HOPr , and its conjugate base, OPr−, are present. This is a
buffer solution. Using the Henderson-Hasselbalch equation where pKa = −log (1.3 ×
10−5) = 4.89:
[base] (0.080)
pH = pKa + log = 4.89 + log = 5.49; assumptions good.
[acid] (0.020)
c. This is a strong acid problem. [H+] = 0.020 M; pH = 1.70
d. Added H+ reacts completely with the best base present, OPr−.
OPr− + H+ → HOPr
Before 0.100 M 0.020 M 0.100 M
After 0.080 0 0.120
A buffer solution results (weak acid + conjugate base). Using the Henderson-
Hasselbalch equation:
[base] (0.080)
[acid] (0.120)
23. a. OH− will react completely with the best acid present, HOPr.
HOPr + OH− → OPr- + H2O

Before 0.100 M 0.020 M 0
After 0.080 0 0.020
A buffer solution results after the reaction. Using the Henderson-Hasselbalch equation:
[base] (0.020)
[acid] (0.080)
b. We have a weak base and a strong base present at the same time. The amount of OH-
added by the weak base will be negligible. To prove it, let’s consider the weak base
equilibrium:
OPr− + H2O ⇌ HOPr + OH− Kb = 7.7 × 10−10
Initial 0.100 M 0 0.020 M
−
x mol/L OPr reacts with H2O to reach equilibrium
Equil. 0.100 − x x 0.020 + x
[OH−] = 0.020 + x ≈ 0.020 M; pOH = 1.70; pH = 12.30; assumption good.
Note: The OH− contribution from the weak base OPr− was negligible (x = 3.9 × 10−9 M as
compared to 0.020 M OH- from the strong base). The pH can be determined by only
considering the amount of strong base present.
c. This is a strong base in water. [OH−] = 0.020 M; pOH = 1.70; pH = 12.30
d. OH− will react completely with HOPr, the best acid present.
HOPr + OH− → OPr− + H2O

Before 0.100 M 0.020 M 0.100 M
After 0.080 0 0.120
Using the Henderson-Hasselbalch equation to solve for the pH of the resulting buffer
solution:
[base] (0.120)
[acid] (0.080)
24. Consider all the results to Exercises 21, 22, and 23:
Solution Initial pH After Added H+ After Added OH−

a 2.96 1.70 4.29
b 8.94 5.49 12.30
c 7.00 1.70 12.30
d 4.89 4.71 5.07
The solution in Exercise 21d is a buffer; it contains both a weak acid (HC3H5O2) and a weak
base (C3H5O2−). Solution d shows the greatest resistance to changes in pH when either a strong
acid or a strong base is added, which is the primary property of buffers.
25. Whenever strong acid is added to a solution, always react the H+ from the strong acid with the
best base present in solution. The best base has the largest Kb value. For a buffer, this will be
the conjugate base (A−) of the acid component of the buffer. The H+ reacts with the conjugate
base, A−, to produce the acid, HA. The assumption for this reaction is that because strong acids
are great at what they do, they are assumed to donate the proton to the conjugate base 100% of
the time. That is, the reaction is assumed to go to completion. Completion is when a reaction
goes until one or both of the reactants runs out. This reaction is assumed to be a stoichiometry
problem like those we solved in Chapter 3 of the text.
Whenever a strong base is added to a buffer, the OH− ions react with the best acid present. This
reaction is also assumed to go to completion. In a buffer, the best acid present is the acid
component of the buffer (HA). The OH− rips a proton away from the acid to produce the
conjugate base of the acid (A−) and H2O. Again, we know strong bases are great at accepting
protons, so we assume this reaction goes to completion. It is assumed to be a stoichiometry
problem like the ones we solved in Chapter 3. Note: For BH+/B type buffers (buffers
composed of a weak base B and its conjugate acid BH+), added OH− reacts to completion with
BH+ to produce B and H2O, while added H+ reacts to completion with B to produce BH+. An
example of a BH+/B type buffer is NH4+/NH3.
26. a. pH = pKa = −log(6.4 × 10−5) = 4.19 since [HBz] = [Bz−], where HBz = C6H5CO2H and
[Bz−] = C6H5CO2−.
b. [Bz−] will increase to 0.120 M and [HBz] will decrease to 0.080 M after OH− reacts
completely with HBz. The Henderson-Hasselbalch equation is derived from the Ka
dissociation reaction.
[Bz − ] (0.120)
pH = pKa + log , pH = 4.19 + log = 4.37; assumptions good.
[HBz] (0.080)
c. Bz− + H2O ⇌ HBz + OH−

Initial 0.120 M 0.080 M 0
Equil. 0.120 − x 0.080 + x x
Kw 1.0 × 10 −14 (0.080 + x)( x) (0.080)( x)
Kb = = −5
= ≈
Ka 6.4 × 10 (0.120 − x) 0.120
x = [OH−] = 2.34 × 10−10 M (carrying extra sig. fig.); assumptions good.
pOH = 9.63; pH = 4.37
d. We get the same answer. Both equilibria involve the two major species, benzoic acid and
benzoate anion. Both equilibria must hold true. Kb is related to Ka by Kw and [OH−] is
related to [H+] by Kw, so all constants are interrelated.
27. Major species: HF, F−, K+, and H2O. K+ has no acidic or basic properties. This is a solution
containing a weak acid and its conjugate base. This is a buffer solution. One appropriate
equilibrium reaction you can use is the Ka reaction of HF, which contains both HF and F−.
However, you could also use the Kb reaction for F− and come up with the same answer.
Alternately, you could use the Henderson-Hasselblach equation to solve for the pH. For this
problem, we will use the Ka reaction and set up an ICE table to solve for the pH.
HF ⇌ F− + H+
Initial 0.60 M 1.00 M ~0
x mol/L HF dissociates to reach equilibrium
Equil. 0.60 − x 1.00 + x x
[F − ][H + ] (1.00 + x)( x) (1.00)( x)

Ka = 7.2 × 10 −4 = = ≈ (assuming x << 0.60)
[HF] 0.60 − x 0.60
x = [H+] = 0.60 × (7.2 × 10−4) = 4.3 × 10 −4 M; assumptions good.
pH = −log(4.3 × 10−4) = 3.37
28. Major species: HONH2 (Kb = 1.1 × 10 −8 ), HONH3+, Cl−, and H2O; Cl− has no acidic/basic
properties. We have a weak base and its conjugate acid present at the same time in solution.
We have a buffer solution. To solve for the pH of a buffer, one can set up an ICE table using
the Ka reaction for HONH3+, or set up an ICE table using the Kb reaction for HONH2, or use
the Henderson-Hasselbalch equation. Using the Henderson-Hasselbalch equation:
[base]  1.0 × 10 −14  [HONH 2 ]

pH = pKa + log = − log  −8 
 + log +
[acid]  1.1 × 10  [HONH 3 ]
 0.100 
pH = −log(9.1 × 10−7) + log   = 6.04 + 0.00 = 6.04
 0.100 
Note that pH = pKa for a buffer solution when [weak base] = [conjugate acid].
29. Major species after NaOH added: HF, F−, K+, Na+, OH−, and H2O. The OH− from the strong
base will react with the best acid present (HF). Any reaction involving a strong base is assumed
to go to completion. Because all species present are in the same volume of solution, we can use
molarity units to do the stoichiometry part of the problem (instead of moles). The stoichiometry
problem is:
OH− + HF → F− + H2O
Before 0.10 mol/1.00 L 0.60 M 1.00 M
Change −0.10 M −0.10 M → +0.10 M Reacts completely
After 0 0.50 1.10
After all the OH− reacts, we are left with a solution containing a weak acid (HF) and its
conjugate base (F−). This is what we call a buffer problem. We will solve this buffer problem
using the Ka equilibrium reaction. One could also use the Kb equilibrium reaction or use the
Henderson-Hasselbalch equation to solve for the pH.
HF ⇌ F− + H+
Initial 0.50 M 1.10 M ~0
x mol/L HF dissociates to reach equilibrium
Equil. 0.50 − x 1.10 + x x
(1.10 + x)( x) (1.10)( x)
Ka = 7.2 × 10 −4 = ≈ , x = [H+] = 3.3 × 10 −4 M; pH = 3.48;
0.50 − x 0.50
assumptions good.
Note: The added NaOH to this buffer solution changes the pH only from 3.37 to 3.48. If the
NaOH were added to 1.0 L of pure water, the pH would change from 7.00 to 13.00.
Major species after HCl added: HF, F−, H+, K+, Cl−, and H2O; the added H+ from the strong
acid will react completely with the best base present (F−).
H+ + F− → HF
0.20 mol
Before 1.00 M 0.60 M
1.00 L
Change −0.20 M −0.20 M → +0.20 M Reacts completely
After 0 0.80 0.80
After all the H+ has reacted, we have a buffer solution (a solution containing a weak acid and
its conjugate base). Solving the buffer problem:
HF ⇌ F− + H+
Initial 0.80 M 0.80 M 0

Equil. 0.80 − x 0.80 + x x
(0.80 + x)( x) (0.80)( x)

Ka = 7.2 × 10 −4 = ≈ , x = [H+] = 7.2 × 10 −4 M; pH = 3.14;
0.80 − x 0.80
assumptions good.
Note: The added HCl to this buffer solution changes the pH only from 3.37 to 3.14. If the HCl
were added to 1.0 L of pure water, the pH would change from 7.00 to 0.70.
30. Major species: H2O, Cl−, Na+, HONH2, HONH3+, and OH−; the added strong base
dominates the initial reaction mixture. Let the OH− react completely with the best acid
present (HONH3+).
HONH3+ + OH− → HONH2 + H2O

Before 0.100 M 0.020 M 0.100 M
After 0.080 0 0.120
A buffer solution results. Using the Henderson-Hasselbalch equation:

 Kw   −14

pH = pKa + log
[base ]
; pK a = − log   = − log  1.0 × 10  = 6.04
 K b , HONH   1.1 × 10 
− 8
[acid ]  2   
[HONH 2 ] (0.120)
pH = 6.04 + log +
= 6.04 + log = 6.04 + 0.18 = 6.22
[HONH 3 ] (0.080)
Major species: H2O, Cl−, HONH2, HONH3+, and H+; the added strong acid domi-
nates the initial reaction mixture. Let the H+ react completely with HONH2, the best
base present.
HONH2 + H+ → HONH3+
Before 0.100 M 0.020 M 0.100 M
After 0.080 0 0.120
A buffer solution results after reaction. Using the Henderson-Hasselbalch equation:

[HONH 2 ] (0.080)
pH = 6.04 + log +
= 6.04 + log = 6.04 − 0.18 = 5.86
[HONH 3 ] (0.120)
31. Ka for H2NNH3+ = K w /K b, H 2 NNH 2 = 1.0 × 10−14/3.0 × 10−6 = 3.3 × 10−9
[H 2 NNH 2 ]  0.40 
pH = pKa + log +
= −log(3.3 × 10−9) + log  = 8.48 + (−0.30) = 8.18
[H 2 NNH 3 ]  0.80 
pH = pKa for a buffer when [acid] = [base]. Here, the acid (H2NNH3+) concentration needs to
decrease, while the base (H2NNH2) concentration needs to increase in order for [H2NNH3+] =
[H2NNH2]. Both of these changes are accomplished by adding a strong base (like NaOH) to
the original buffer. The added OH− from the strong base converts the acid component of the
buffer into the conjugate base. Here, the reaction is H2NNH3+ + OH− → H2NNH2 + H2O.
Because a strong base is reacting, the reaction is assumed to go to completion. The following
set-up determines the number of moles of OH−(x) that must be added so that mol H2NNH3+ =
mol H2NNH2 . When mol acid = mol base in a buffer, then [acid] = [base] and pH = pKa.
H2NNH3+ + OH− → H2NNH2 + H2O

Before 1.0 L × 0.80 mol/L x 1.0 L × 0.40 mol/L
Change −x −x → +x Reacts completely
After 0.80 − x 0 0.40 + x
We want mol H2NNH3+ = mol H2NNH2. So:
0.80 − x = 0.40 + x, 2x = 0.40, x = 0.20 mol OH−
When 0.20 mol OH− is added to the initial buffer, mol H2NNH3+ is decreased to 0.60 mol,
while mol H2NNH2 is increased to 0.60 mol. Therefore, 0.20 mol of NaOH must be added to
the initial buffer solution in order to produce a solution where pH = pKa.
[OCl − ]  0.90 
32. pH = pKa + log = −log(3.5 × 10−8) + log  = 7.46 + 0.65 = 8.11
[HOCl]  0.20 
pH = pKa when [HOCl] = [OCl−] (or when mol HOCl = mol OCl−). Here, the moles of the
base component of the buffer must decrease, while the moles of the acid component of the
buffer must increase in order to achieve a solution where pH = pKa. Both of these changes
occur when a strong acid (like HCl) is added. Let x = mol H+ added from the strong acid
HCl.
H+ + OCl− → HOCl
Before x 1.0 L × 0.90 mol/L 1.0 L × 0.20 mol/L
After 0 0.90 − x 0.20 + x
We want mol HOCl = mol OCl−. Therefore:
0.90 − x = 0.20 + x, 2x = 0.70, x = 0.35 mol H+
When 0.35 mol H+ is added, mol OCl− is decreased to 0.55 mol, while the mol HOCl is
increased to 0.55 mol Therefore, 0.35 mol of HCl must be added to the original buffer
solution in order to produce a solution where pH = pKa.
1 mol HC 7 H 5 O 2
21.5 g HC 7 H 5 O 2 ×
122.12 g
33. [HC7H5O2] = = 0.880 M
0.2000 L
−
1 mol NaC 7 H 5 O 2 1 mol C 7 H 5 O 2
37.7 g NaC 7 H 5 O 2 × ×
144.10 g mol NaC 7 H 5 O 2
[C7H5O2−] = = 1.31 M
0.2000 L
We have a buffer solution since we have both a weak acid and its conjugate base present at the
same time. One can use the Ka reaction or the Kb reaction to solve. We will use the Ka reaction
for the acid component of the buffer.
HC7H5O2 ⇌ H+ + C7H5O2−
Initial 0.880 M ~0 1.31 M
x mol/L of HC7H5O2 dissociates to reach equilibrium
Equil. 0.880 – x x 1.31 + x
x(1.31 + x) x(1.31)
Ka = 6.4 × 10 −5 = ≈ , x = [H+] = 4.3 × 10 −5 M
0.880 − x 0.880
pH = −log(4.3 × 10 −5 ) = 4.37; assumptions good.
Alternatively, we can use the Henderson-Hasselbalch equation to calculate the pH of buffer

solutions.
−
[base] [C H O ]
pH = pKa + log = pKa + log 7 5 2
[acid] [HC 7 H 5 O 2 ]
 1.31 
pH = −log(6.4 × 10 −5 ) + log   = 4.19 + 0.173 = 4.36
 0.880 
Within round-off error, this is the same answer we calculated solving the equilibrium
problem using the Ka reaction.
The Henderson-Hasselbalch equation will be valid when an assumption of the type 1.31 + x ≈
1.31 that we just made in this problem is valid. From a practical standpoint, this will almost
always be true for useful buffer solutions. If the assumption is not valid, the solution will have
such a low buffering capacity that it will be of no use to control the pH. Note: The Henderson-
Hasselbalch equation can only be used to solve for the pH of buffer solutions.
1 mol NH 4 Cl
34. 50.0 g NH4Cl × = 0.935 mol NH4Cl added to 1.00 L; [NH4+] = 0.935 M
53.49 g NH 4 Cl
Using the Henderson Hasselbalch equation to solve for the pH of this buffer solution:
[ NH 3 ]  0.75 
pH = pKa + log +
= −log(5.6 × 10 −10 ) + log   = 9.25 − 0.096 = 9.15
[ NH 4 ]  0.935 
Kw 1.0 × 10 −14
35. C5H5NH+ ⇌ H+ + C5H5N Ka = = = 5.9 × 10−6
Kb 1.7 × 10 −9
pKa = −log(5.9 × 10−6) = 5.23
We will use the Henderson-Hasselbalch equation to calculate the concentration ratio

necessary for each buffer.
[base] [C 5 H 5 N ]
pH = pKa + log , pH = 5.23 + log
[acid] [C 5 H 5 NH + ]
[C 5 H 5 N ] [C 5 H 5 N ]
a. 4.50 = 5.23 + log b. 5.00 = 5.23 + log
[C 5 H 5 NH + ] [C 5 H 5 NH + ]
[C 5 H 5 N ] [C 5 H 5 N ]
log = −0.73 log = −0.23
[C 5 H 5 NH + ] [C 5 H 5 NH + ]
[C 5 H 5 N ] [C 5 H 5 N ]
= 10−0.73 = 0.19 = 10−0.23 = 0.59
[C 5 H 5 NH + ] [C 5 H 5 NH + ]
[C 5 H 5 N ] [C 5 H 5 N ]
c. 5.23 = 5.23 + log d. 5.50 = 5.23 + log
[C 5 H 5 NH + ] [C 5 H 5 NH + ]
[C 5 H 5 N ] [C 5 H 5 N ]
= 100.0 = 1.0 = 100.27 = 1.9
[C 5 H 5 NH + ] [C 5 H 5 NH + ]
36. Added OH− converts HC2H3O2 into C2H3O2−: HC2H3O2 + OH− → C2H3O2− + H2O
From this reaction, the moles of C2H3O2− produced equal the moles of OH− added. Also, the
total concentration of acetic acid plus acetate ion must equal 2.0 M (assuming no volume
change on addition of NaOH). Summarizing for each solution:
[C2H3O2−] + [HC2H3O] = 2.0 M and [C2H3O2−] produced = [OH−] added

− −
[C 2 H 3 O 2 ] [C H O ]
a. pH = pKa + log ; for pH = pKa, log 2 3 2 =0
[HC 2 H 3O 2 ] [HC 2 H 3O 2 ]
−
[C 2 H 3 O 2 ]
Therefore, = 1.0 and [C2H3O2−] = [HC2H3O2].
[HC 2 H 3O 2 ]
Because [C2H3O2−] + [HC2H3O2] = 2.0 M:
[C2H3O2−] = [HC2H3O2] = 1.0 M = [OH−] added
To produce a 1.0 M C2H3O2− solution, we need to add 1.0 mol of NaOH to 1.0 L of the
2.0 M HC2H3O2 solution. The resulting solution will have pH = pKa = 4.74.
− −
[C 2 H 3 O 2 ] [C 2 H 3 O 2 ]
b. 4.00 = 4.74 + log , = 10−0.74 = 0.18
[HC 2 H 3O 2 ] [HC 2 H 3O 2 ]
[C2H3O2−] = 0.18[HC2H3O2] or [HC2H3O2] = 5.6[C2H3O2−]
Because [C2H3O2−] + [HC2H3O2] = 2.0 M:

2.0
[C2H3O2−] + 5.6[C2H3O2−] = 2.0 M, [C2H3O2−] = = 0.30 M = [OH−] added
6.6
We need to add 0.30 mol of NaOH to 1.0 L of 2.0 M HC2H3O2 solution to produce 0.30
M C2H3O2−. The resulting solution will have pH = 4.00.
− −
[C H O ] [C 2 H 3 O 2 ]
c. 5.00 = 4.74 + log 2 3 2 , = 100.26 = 1.8
[HC 2 H 3O 2 ] [HC 2 H 3O 2 ]
1.8[HC2H3O2] = [C2H3O2−] or [HC2H3O2] = 0.56[C2H3O2−]
1.56[C2H3O2−] = 2.0 M, [C2H3O2−] = 1.3 M = [OH−] added
We need to add 1.3 mol of NaOH to 1.0 L of 2.0 M HC2H3O2 to produce a solution with
pH = 5.00.
37. When H+ is added, it converts C2H3O2− into HC2H3O2: C2H3O2− + H+ → HC2H3O2. From
this reaction, the moles of HC2H3O2 produced must equal the moles of H+ added and the total
concentration of acetate ion + acetic acid must equal 1.0 M (assuming no volume change).
Summarizing for each solution:
[C2H3O2−] + [HC2H3O2] = 1.0 M and [HC2H3O2] = [H+] added

−
[C 2 H 3 O 2 ]
a. pH = pKa + log ; for pH = pKa, [C2H3O2−] = [HC2H3O2].
[HC 2 H 3O 2 ]
For this to be true, [C2H3O2−] = [HC2H3O2] = 0.50 M = [H+] added, which means that
0.50 mol of HCl must be added to 1.0 L of the initial solution to produce a solution with
pH = pKa.
− −
[C 2 H 3 O 2 ] [C 2 H 3 O 2 ]
b. 4.20 = 4.74 + log , = 10 −0.54 = 0.29
[HC 2 H 3O 2 ] [HC 2 H 3O 2 ]
[C2H3O2−] = 0.29[HC2H3O2]; 0.29[HC2H3O2] + [HC2H3O2] = 1.0 M
[HC2H3O2] = 0.78 M = [H+] added
0.78 mol of HCl must be added to produce a solution with pH = 4.20.

− −
[C 2 H 3 O 2 ] [C 2 H 3 O 2 ]
c. 5.00 = 4.74 + log , = 100.26 = 1.8
[HC 2 H 3O 2 ] [HC 2 H 3O 2 ]
[C2H3O2−] = 1.8[HC2H3O2]; 1.8[HC2H3O2] + [HC2H3O2] = 1.0 M
[HC2H3O2] = 0.36 M = [H+] added
0.36 mol of HCl must be added to produce a solution with pH = 5.00.
− −
[C H O ] [C H O ]
38. pH = pKa + log 2 3 2 , 4.00 = −log(1.8 × 10 −5 ) + log 2 3 2
[HC 2 H 3O 2 ] [HC 2 H 3O 2 ]
−
[C 2 H 3 O 2 ]
= 0.18; this is also equal to the mole ratio between C2H3O2− and HC2H3O2.
[HC 2 H 3O 2 ]
Let x = volume of 1.00 M HC2H3O2 and y = volume of 1.00 M NaC2H3O2
x + y = 1.00 L, x = 1.00 – y
x(1.00 mol/L) = mol HC2H3O2; y(1.00 mol/L) = mol NaC2H3O2 = mol C2H3O2−
y y
Thus: = 0.18 or = 0.18; solving: y = 0.15 L, so x = 1.00 − 0.15 = 0.85 L.
x 1.00 − y
We need 850 mL of 1.00 M HC2H3O2 and 150 mL of 1.00 M NaC2H3O2 to produce a buffer
solution at pH = 4.00.
−
[C 2 H 3 O 2 ]
39. pH = pKa + log ; pKa = −log(1.8 × 10−5) = 4.74
[HC 2 H 3O 2 ]
Because the buffer components, C2H3O2− and HC2H3O2, are both in the same volume of
water, the concentration ratio of [C2H3O2−]/[HC2H3O2] will equal the mole ratio of mol
C2H3O2−/mol HC2H3O2.
−
mol C 2 H 3O 2 0.200 mol
5.00 = 4.74 + log ; mol HC2H3O2 = 0.5000 L × = 0.100 mol
mol HC 2 H 3O 2 L
− −
mol C 2 H 3O 2 mol C 2 H 3O 2
0.26 = log , = 100.26 = 1.8, mol C2H3O2− = 0.18 mol
0.100 mol 0.100 mol
82.03 g
Mass NaC2H3O2 = 0.18 mol NaC2H3O2 × = 15 g NaC2H3O2
mol
0.010 mol
40. [H+] added = = 0.040 M; the added H+ reacts completely with NH3 to form NH4+.
0.2500 L
a. NH3 + H+ → NH4+
Before 0.050 M 0.040 M 0.15 M
After 0.010 0 0.19
A buffer solution still exists after H+ reacts completely. Using the Henderson-
[ NH 3 ]  0.010 
pH = pKa + log = −log(5.6 × 10−10) + log 
+  = 9.25 + (−1.28) = 7.97
[ NH 4 ]  0.19 
b. NH3 + H+ → NH4+
Before 0.50 M 0.040 M 1.50 M
After 0.46 0 1.54
[ NH 3 ]  0.46 
A buffer solution still exists. pH = pKa + log +
, 9.25 + log   = 8.73
[ NH 4 ]  1.54 
The two buffers differ in their capacity and not their initial pH (both buffers had an initial
pH = 8.77). Solution b has the greatest capacity since it has the largest concentrations of
weak acid and conjugate base. Buffers with greater capacities will be able to absorb more
added H+ or OH−.
41. a. pKb for C6H5NH2 = −log(3.8 × 10−10) = 9.42; pKa for C6H5NH3+ = 14.00 − 9.42 = 4.58
[C 6 H 5 NH 2 ] 0.50 M
pH = pKa + log +
, 4.20 = 4.58 + log +
[C 6 H 5 NH 3 ] [C 6 H 5 NH 3 ]
0.50 M
−0.38 = log +
, [C6H5NH3+] = [C6H5NH3Cl] = 1.2 M
[C 6 H 5 NH 3 ]
1 mol NaOH 1 mol OH − 0.10 mol

b. 4.0 g NaOH × × = 0.10 mol OH−; [OH−] = = 0.10 M
40.00 g mol NaOH 1.0 L
C6H5NH3+ + OH− → C6H5NH2 + H2O

Before 1.2 M 0.10 M 0.50 M
Change −0.10 −0.10 → +0.10
After 1.1 0 0.60
 0.60 
A buffer solution exists. pH = 4.58 + log   = 4.32
 1.1 
− −
[ NO 2 ] [ NO 2 ]
42. pH = pKa + log , 3.55 = −log(4.0 × 10−4) + log
[HNO 2 ] [HNO 2 ]
− −
[ NO 2 ] [ NO 2 ]
3.55 = 3.40 + log , = 100.15 = 1.4
[HNO 2 ] [HNO 2 ]
Let x = volume (L) HNO2 solution needed, then 1.00 − x = volume of NaNO2 solution
needed to form this buffer solution.
0.50 mol NaNO 2
− (1.00 − x) × 0.50 − (0.50) x
[ NO 2 ] L
= 1.4 = =
[HNO 2 ] 0.50 mol HNO 2 (0.50) x
x×
L
(0.70)x = 0.50 − (0.50)x , (1.20)x = 0.50, x = 0.42 L
We need 0.42 L of 0.50 M HNO2 and 1.00 − 0.42 = 0.58 L of 0.50 M NaNO2 to form a pH =
3.55 buffer solution.
2−
[base] [HPO 4 ]
43. a. pH = pKa + log , 7.15 = −log(6.2 × 10 −8 ) + log −
[acid] [H 2 PO 4 ]
[HPO 4 2− ] [HPO 4 2− ] [H 2 PO 4 − ] 1
7.15 = 7.21 + log −
, −
= 10 −0.06
= 0.9, 2−
= = 1.1 ≈ 1
[H 2 PO 4 ] [H 2 PO 4 ] [HPO 4 ] 0.9
b. A best buffer has approximately equal concentrations of weak acid and conjugate base, so
pH ≈ pKa for a best buffer. The pKa value for a H3PO4/H2PO4− buffer is −log(7.5 × 10 −3 )
= 2.12. A pH of 7.15 is too high for a H3PO4/H2PO4− buffer to be effective. At this high of
pH, there would be so little H3PO4 present that we could hardly consider it a buffer; this
solution would not be effective in resisting pH changes, especially when a strong base is
added.
[HCO 3 − ] [HCO 3 − ]
44. pH = pKa + log , 7.40 = −log(4.3 × 10−7) + log
[H 2 CO 3 ] 0.0012
[HCO 3 − ] [HCO 3 − ]
log = 7.40 – 6.37 = 1.03, = 101.03, [HCO3−] = 1.3 × 10−2 M
0.0012 0.0012
[HCO 3 − ]
45. At pH = 7.40: 7.40 = −log(4.3 × 10 ) + log
−7
[H 2 CO 3 ]
[HCO 3 − ] [HCO 3 − ] [H 2 CO 3 ]
log = 7.40 – 6.37 = 1.03, = 101.03, = 10−1.03 = 0.093
[H 2 CO 3 ] [H 2 CO 3 ] [HCO 3 − ]
[HCO 3 − ] [HCO 3 − ]
At pH = 7.35: log = 7.35 – 6.37 = 0.98, = 100.98
[H 2 CO 3 ] [H 2 CO 3 ]
[H 2 CO 3 ]
−
= 10−0.98 = 0.10
[HCO 3 ]
The [H2CO3] : [HCO3−] concentration ratio must increase from 0.093 to 0.10 in order for the
onset of acidosis to occur.
46. The reaction OH− + CH3NH3+ → CH3NH2 + H2O goes to completion for solutions a, c, and
d (no reaction occurs between the species in solution b because both species are bases). After
the OH− reacts completely, there must be both CH3NH3+ and CH3NH2 in solution for it to be a
buffer. The important components of each solution (after the OH− reacts completely) is(are):
a. 0.05 M CH3NH2 (no CH3NH3+ remains, no buffer)

b. 0.05 M OH− and 0.1 M CH3NH2 (two bases present, no buffer)
c. 0.05 M OH− and 0.05 M CH3NH2 (too much OH− added, no CH3NH3+ remains, no
buffer)
d. 0.05 M CH3NH2 and 0.05 M CH3NH3+ (a buffer solution results)
Only the combination in mixture d results in a buffer. Note that the concentrations are halved
from the initial values. This is so because equal volumes of two solutions were added together,
which halves the concentrations.
47. a. No; a solution of a strong acid (HNO3) and its conjugate base (NO3−) is not generally
considered a buffer solution.
b. No; two acids are present (HNO3 and HF), so it is not a buffer solution.
c. H+ reacts completely with F−. Since equal volumes are mixed, the initial concentrations in
the mixture are 0.10 M HNO3 and 0.20 M NaF.
H+ + F− → HF
Before 0.10 M 0.20 M 0
After 0 0.10 0.10
After H+ reacts completely, a buffer solution results; that is, a weak acid (HF) and its
conjugate base (F−) are both present in solution in large quantities.
d. No; a strong acid (HNO3) and a strong base (NaOH) do not form buffer solutions. They
will neutralize each other to form H2O.
48. Because we have added two solutions together, the concentration of each reagent has
changed. What hasn’t changed is the moles or millimoles of each reagent. Let’s determine
the millimoles of each reagent present by multiplying the volume in milliters by the molarity
in units of mmol/mL.
100.0 mL × 0.100 M = 10.0 mmol NaF; 100.0 mL × 0.025 M = 2.5 mmol HCl
H+ + F− → HF; 2.5 mmol H+ converts 2.5 mmol F− into 2.5 mmol HF. After the reaction, a
buffer solution results containing 2.5 mmol HF and (10.0 − 2.5 =) 7.5 mmol F− in 200.0 mL
of solution.
[F − ]  7.5 mmol / 200.0 mL 
pH = pKa + log = 3.14 + log   = 3.62; assumptions good.
[HF]  2.5 mmol / 200.0 mL 
49. A best buffer has large and equal quantities of weak acid and conjugate base. Because [acid]
[base]
= [base] for a best buffer, pH = pKa + log = pKa + 0 = pKa (pH ≈ pKa for a best
[acid]
buffer).
The best acid choice for a pH = 7.00 buffer would be the weak acid with a pKa close to 7.0 or
Ka ≈ 1 × 10−7. HOCl is the best choice in Table 7.2 (Ka = 3.5 × 10−8; pKa = 7.46). To make
this buffer, we need to calculate the [base]/[acid] ratio.
[base] [OCl − ]
7.00 = 7.46 + log , = 10−0.46 = 0.35
[acid] [HOCl]
Any OCl−/HOCl buffer in a concentration ratio of 0.35 : 1 will have a pH = 7.00. One
possibility is [NaOCl] = 0.35 M and [HOCl] = 1.0 M.
50. For a pH = 5.00 buffer, we want an acid with a pKa close to 5.00. For a conjugate acid-base
pair, 14.00 = pKa + pKb. So for a pH = 5.00 buffer, we want the base to have a pKb close to
(14.0 − 5.0 =) 9.0 or a Kb close to 1 × 10−9. The best choice in Table 7.3 is pyridine (C5H5N)
with Kb = 1.7 × 10−9.
[base] K 1.0 × 10 −14
pH = pKa + log ; Ka = w = = 5.9 × 10−6
[acid] Kb 1.7 × 10 −9
[base] [C 5 H 5 N ]
5.00 = −log(5.9 × 10-6) + log , = 10−0.23 = 0.59
[acid] [C 5 H 5 NH + ]
There are many possibilities to make this buffer. One possibility is a solution of [C5H5N] =
0.59 M and [C5H5NHCl] = 1.0 M. The pH of this solution will be 5.00 because the base to
acid concentration ratio is 0.59 : 1.
51. To solve for [KOCl], we need to use the equation derived in Section 8.3 of the text on the
exact treatment of buffered solutions. The equation is:
 [ H + ]2 − K w 
[H + ] [A − ]0 + 

 [H + ] 
Ka =
[ H + ]2 − K w
[HA]0 −
[H + ]
Because pH = 7.20, [H+] = 10−7.20 = 6.3 × 10−8 M.
 (6.3 × 10 −8 ) 2 − (1.0 × 10 −14 ) 
6.3 × 10 −8  [OCl − ] + 

 6.3 × 10 −8 
Ka = 3.5 × 10−8 =
(6.3 × 10 −8 ) 2 − (1.0 × 10 −14 )
1.0 × 10 −6 −
6.3 × 10 −8
6.3 × 10 −8 ([OCl − ] − 9.57 × 10 −8 )

3.5 × 10−8 = (Carrying extra significant figures.)
(1.0 × 10 −6 ) + (9.57 × 10 −8 )
3.83 × 10−14 = 6.3 × 10-8([OCl−] − 9.57 × 10−8), [OCl−] = [KOCl] = 7.0 × 10−7 M
[BH + ][OH − ]
52. B + H2O ⇌ BH+ + OH− Kb =
[B]
The equation for the exact treatment of B/BHCl type buffers would be analogous to the
equation for HA/NaA type buffers. The equation is:
 [OH − ]2 − K w 
[OH − ] [BH + ]0 + 

 [OH − ] 
Kb =
[OH − ]2 − K w
[B]0 −
[OH − ]
Solving the buffer problem using the regular procedures:
HONH2 + H2O ⇌ HONH3+ + OH− Kb = 1.1 × 10−8

Initial 1.0 × 10−4 M 1.0 × 10−5 M ~0
x mol/L of HONH2 reacts with H2O to reach equilibrium
Change −x +x +x
Equil. 1.0 × 10 − x
−4 −5
1.0 × 10 + x x
+
[HONH 3 ][OH − ] (1.0 × 10 −5 + x) x (1.0 × 10 −5 ) x
Kb = 1.1 × 10−8 = = ≈
[HONH 2 ] (1.0 × 10 − 4 − x) 1.0 × 10 − 4
(Assuming x << 1.0 × 10−5.)
x = [OH−] = 1.1 × 10−7 M; assumption that x << 1.0 × 10−5 is good (x is 1.1% of 1.0 × 10−5).
In the regular procedure to solve the buffer problem, the problem reduced down to the
expression:
+
[HONH 3 ] 0 [OH − ]
Kb =
[HONH 2 ] 0
This expression holds if x is negligible as compared to [HONH3+]0 and [HONH2]0 as it was in

this problem. Now we want to know if we need to worry about the contribution of OH− from
water. From the equation for the exact treatment of buffers, if ([OH−]2 − Kw) / [OH−] is much
less than [HONH3+]0 and [HONH2]0, then the exact equation reduces to:
+
[OH − ][HONH 3 ]0
Kb =
[HONH 2 ]0
This is the same expression we ended up with to solve the problem using the regular
procedures. Checking the neglected term using the [OH−] calculated above:
[OH − ]2 − K w (1.1 × 10 −7 ) 2 − (1.0 × 10 −14 )
= = 1.9 × 10−8
[OH − ] 1.1 × 10 −7
This is indeed much smaller than [HONH3+]0 and [HONH2]0 (1.9 × 10−8 is 0.19% of 1.0
× 10−5). So for this problem we would calculate the same [OH−] using the exact equation as
we calculated using the regular procedures. In general, we only need to use the exact equation
when the buffering materials have a concentration of 10−6 M or less.
53. Using regular procedures, pH = pKa = −log(1.6 × 10−7) = 6.80 since [A−]0 = [HA]0 in this buffer
solution. However, the pH is very close to that of neutral water, so maybe we need to consider
the H+ contribution from water. Another problem with this answer is that x (= [H+]) is not small
as compared with [HA]0 and [A−]0 , which was assumed when solving using the regular
procedures. Because the concentrations of the buffer components are less than 10−6 M, let us
use the expression for the exact treatment of buffers to solve.
 [ H + ]2 − K w 
[H + ] [A − ]0 + 

 [H + ]  =
Ka = 1.6 × 10−7 =
[ H + ]2 − K w
[HA]0 −
[H + ]
 [H + ]2 − (1.0 × 10 −14 ) 
[H + ] 5.0 × 10 −7 + 

 [H + ] 
[H + ]2 − (1.0 × 10 −14 )
5.0 × 10 −7 −
[H + ]
Solving exactly requires solving a cubic equation. Instead, we will use the method of
successive approximations where our initial guess for [H+] = 1.6 × 10−7 M (the value obtained
using the regular procedures).
 (1.6 × 10 −7 ) 2 − (1.0 × 10 −14 ) 
[H + ] 5.0 × 10 −7 + 

−7  1.6 × 10 −7  , [H+] = 1.1 × 10−7
1.6 × 10 =
(1.6 × 10 −7 ) 2 − (1.0 × 10 −14 )
5.0 × 10 −7 −
1.6 × 10 −7
We continue the process using 1.1 × 10−7 as our estimate for [H+]. This gives [H+] = 1.5 ×
10−7. We continue the process until we get a self consistent answer. After three more
iterations, we converge on [H+] = 1.3 × 10−7 M. Solving for the pH:
pH = −log(1.3 × 10−7) = 6.89
Note that if we were to solve this problem exactly (using the quadratic formula) while
ignoring the H+ contribution from water, the answer comes out to [H+] = 1.0 × 10−7 M. We
get a significantly different answer when we consider the H+ contribution from H2O.
Acid-Base Titrations
54. a. The red plot is the pH curve for the strong acid and the blue plot is the pH curve for the
weak acid. The pH at the equivalence point is 7.00 for the strong acid-strong base titration,
while the pH is greater than 7.00 if a weak acid is titrated. Another point one could look
at is the initial point. Because both acids have the same concentration, the strong acid
curve will be at the lowest initial pH. Actually, any point at any volume up to the
equivalence point for the strong acid plot will have a lower pH than the weak acid plot
(assuming equal concentrations and volumes). Another difference would be the pH at the
halfway point to equivalence. For the weak acid titration, the pH of solution equals the
pKa value for the weak acid at the halfway point to equivalence; this is not the case when
a strong acid is titrated.
b. A buffer is a solution that resists pH change. From this definition, both titrations have
regions where the pH doesn’t change much on addition of strong base, so both could be
labeled to have buffer regions. However, we don’t normally include strong acids as a
component of buffer solutions. Strong acids certainly can absorb added OH− by reacting
with it to form water. But when more strong acid is added, the H+ concentration increases
steadily; there is nothing present in a strong acid solution to react with added H+.
This is not the case in the weak acid-strong base titration. After some OH− has been added,
some weak acid is converted into its conjugate base. We now have a typical buffer solution
because there are significant amounts of weak acid and conjugate base present at the same
time. The buffer region extends from a little past the initial point in the titration up to just
a little before the equivalence point. This entire region is a buffer region because both the
weak acid and conjugate base are present in significant quantities in this region.
c. True; HA + OH− → A− + H2O; both reactions have the same neutralization reaction.
In both cases, the equivalence point is reached when enough OH− has been added to exactly
react with the acid present initially. Because all acid concentrations and volumes are the
same, we have equal moles of each acid which requires the same moles of OH− to reach
the equivalence point. Therefore, each acid requires the same volume of 0.10 M NaOH to
reach the equivalence point.
d. False; the pH for the strong acid-strong base titration will be 7.00 at the equivalence point.
The pH for the weak acid-strong base titration will be greater than 7.00 at the equivalence
point. In both titrations, the major species present at the equivalence points are Na+, H2O,
and the conjugate base of the acid titrated. Because the conjugate base of a strong acid has
no basic characteristics, pH = 7.00 at the equivalence point. However, the conjugate base
of a weak acid is a weak base. A weak base is present at the equivalence point of a weak
acid-strong base titration, so the pH is basic (pH > 7.0).
55. a. Let’s call the acid HB, which is a weak acid. When HB is present in the beakers, it exists
in the undissociated form, making it a weak acid. A strong acid would exist as separate H+
and B− ions.
b. Beaker a contains 4 HB molecules and 2 B− ions, beaker b contains 6 B− ions, beaker c

contains 6 HB molecules, beaker d contains 6 B− and 6 OH− ions, and beaker e contains 3
HB molecules and 3 B− ions. HB + OH− → B− + H2O; this is the neutralization reaction
that occurs when OH− is added. We start off the titration with a beaker full of weak acid
(beaker c). When some OH− is added, we convert some weak acid HB into its conjugate
base B− (beaker a). At the halfway point to equivalence, we have converted exactly one-
half of the initial amount of acid present into its conjugate base (beaker e). We finally
reach the equivalence point when we have added just enough OH− to convert all of the acid
present initially into its conjugate base (beaker b). Past the equivalence point, we have
added an excess of OH−, so we have excess OH− present as well as the conjugate base of
the acid produced from the neutralization reaction (beaker d). The order of the beakers
from start to finish is:
beaker c → beaker a → beaker e → beaker b → beaker d
c. pH = pKa when a buffer solution is present that has equal concentrations of the weak acid
and conjugate base. This is beaker e.
d. The equivalence point is when just enough OH− has been added to exactly react with all of
the acid present initially. This is beaker b.
e. Past the equivalence, the pH is dictated by the concentration of excess OH− added from the
strong base. We can ignore the amount of hydroxide added by the weak conjugate base
that is also present. This is beaker d.
56. (f) all points after

stoichiometric point
(a) and (e)
pH
(c)
(d) (b)
mL base
HA + OH− → A− + H2O; added OH− from the strong base converts the weak acid HA into its
conjugate base A−. Initially before any OH− is added (point d), HA is the dominant species
present. After OH− is added, both HA and A− are present, and a buffer solution results (region
b). At the equivalence point (points a and e), exactly enough OH- has been added to convert
all the weak acid HA into its conjugate base A−. Past the equivalence point (region f), excess
OH− is present. For the answer to part b, we included almost the entire buffer region. The
maximum buffer region (or the region which is the best buffer solution) is around the halfway
point to equivalence (point c). At this point, enough OH− has been added to convert exactly
one-half of the weak acid present initially into its conjugate base, so [HA] = [A−] and pH =
pKa. A best buffer has about equal concentrations of weak acid and conjugate base present.
57.
(d)
(c)
(b)
pH
(a) and (e)
(f) all points after

stoichiometric point
mL acid
B + H+ → BH+; added H+ from the strong acid converts the weak base B into its conjugate acid
BH+. Initially, before any H+ is added (point d), B is the dominant species present. After H+
is added, both B and BH+ are present, and a buffered solution results (region b). At the
equivalence point (points a and e), exactly enough H+ has been added to convert all the weak
base present initially into its conjugate acid BH+. Past the equivalence point (region f), excess
H+ is present. For the answer to b, we included almost the entire buffer region. The maximum
buffer region is around the halfway point to equivalence (point c), where [B] = [BH+]. Here,
pH = pKa , which is a characteristic of a best buffer.
58. Let’s review the strong acid-strong base titration using the example (case study) covered in
Section 8.5 of the text. The example used was the titration of 50.0 mL of 0.200 M HNO3 titrated
by 0.100 M NaOH. See Fig. 8.1 for the titration curve. Here are the important points.
a. Initially, before any strong base has been added. Major species: H+, NO3−, and H2O. To
determine the pH, determine the [H+] in solution after the strong acid has completely
dissociated, as we always do for strong acid problems.
b. After some strong base has been added, up to the equilivance point. For our example, this
is from just after 0.00 mL NaOH added up to just before 100.0 mL NaOH added. Major
species before any reaction: H+, NO3−, Na+, OH−, and H2O. Na+ and NO3− have no acidic
or basic properties. In this region, the OH− from the strong base reacts with some of the H+
from the strong acid to produce water (H+ + OH− → H2O). As is always the case when
something strong reacts, we assume the reaction goes to completion. Major species after
reaction: H+, NO3−, Na+, and H2O: To determine the pH of the solution, we first determine
how much of the H+ is neutralized by the OH−. Then we determine the excess [H+] and
take the –log of this quantity to determine pH. From 0.1 to 99.9 mL NaOH added, the
excess H+ from the strong acid determines the pH.
c. The equivalence point (100.0 mL NaOH added). Major species before reaction: H+, NO3−,
Na+, OH−, and H2O. Here, we have added just enough OH− to neutralize all of the H+ from
the strong acid (moles OH− added = moles H+ present). After the stoichiometry reaction
(H+ + OH− → H2O), both H+ and OH− have run out (this is the definition of the equivalence
point). Major species after reaction: Na+, NO3−, and H2O. All we have in solution are some
ions with no acidic or basic properties (NO3− and Na+ in H2O). The pH = 7.00 at the
equivalence point of a strong acid-strong base titration.
d. Past the equivalence point (volume of NaOH added > 100.0 mL). Major species before
reaction H+, NO3−, Na+, OH−, and H2O. After the stoichiometry reaction goes to completion
(H+ + OH− → H2O), we have excess OH− present. Major species after reaction: OH−, Na+,
NO3−, and H2O. We determine the excess [OH−] and convert this into the pH. After the
equivalence point, the excess OH− from the strong base determines the pH.
See Fig. 8.2 for a titration curve of a strong base by a strong acid. The stoichiometry problem
is still the same, H+ + OH− → H2O, but what is in excess after this reaction goes to completion
is the reverse of the strong acid-strong base titration. The pH up to just before the equivalence
point is determined by the excess OH− present. At the equivalence point, pH = 7.00 because
we have added just enough H+ from the strong acid to react with all the OH− from the strong
base (moles of base present = moles of acid added). Past the equivalence point, the pH is
determined by the excess H+ present. As can be seen from Figs. 8.1 and 8.2, both strong by
strong titrations have pH = 7.00 at the equivalence point, but the curves are the reverse of each
other before and after the equivalence point.
59. Titration i is a strong acid titrated by a strong base. The pH is very acidic until just before the
equivalence point; at the equivalence point, pH = 7.00; and past the equivalence the pH is very
basic. Titration ii is a strong base titrated by a strong acid. Here the pH is very basic until just
before the equivalence point; at the equivalence point, pH = 7.00; and past the equivalence
point, the pH is very acidic. Titration iii is a weak base titrated by a strong acid. The pH starts
out basic because a weak base is present. However, the pH will not be as basic as in titration ii,
where a strong base is titrated. The pH drops as HCl is added; then at the halfway point to
equivalence, pH = pKa. Because Kb = 4.4 × 10 −4 for CH3NH2, CH3NH3+ has Ka = Kw/Kb = 2.3
× 10 −11 and pKa = 10.64. So, at the halfway point to equivalence for this weak base-strong acid
titration, pH = 10.64. The pH continues to drop as HCl is added; then at the equivalence point
the pH is acidic (pH < 7.00) because the only important major species present is a weak acid
(the conjugate acid of the weak base). Past the equivalence point the pH becomes more acidic
as excess HCl is added. Titration iv is a weak acid titrated by a strong base. The pH starts off
acidic, but not nearly as acidic as the strong acid titration (i). The pH increases as NaOH is
added; then, at the halfway point to equivalence, pH = pKa for HF = −log(7.2 × 10 −4 ) = 3.14.
The pH continues to increase past the halfway point; then at the equivalence point, the pH is
basic (pH > 7.0) because the only important major species present is a weak base (the conjugate
base of the weak acid). Past the equivalence point, the pH becomes more basic as excess NaOH
is added.
a. All require the same volume of titrant to reach the equivalence point. At the equivalence
point for all these titrations, moles acid = moles base (MAVA = MBVB). Because all the
molarities and volumes are the same in the titrations, the volume of titrant will be the same
(50.0 mL titrant added to reach equivalence point).
b. Increasing initial pH: i < iv < iii < ii; the strong acid titration has the lowest pH, the weak
acid titration is next, followed by the weak base titration, with the strong base titration
having the highest pH.
c. i < iv < iii < ii; the strong acid titration has the lowest pH at the halfway point to
equivalence, and the strong base titration has the highest halfway point pH. For the weak
acid titration, pH = pKa = 3.14, and for the weak base titration, pH = pKa = 10.64.
d. Equivalence point pH: iii < ii = i < iv; the strong-by-strong titrations have pH = 7.00 at
the equivalence point. The weak base titration has an acidic pH at the equivalence point,
and a weak acid titration has a basic equivalence point pH.
The only different answer when the weak acid and weak base are changed would be for
part c. This is for the halfway point to equivalence, where pH = pKa.
HOC6H5; Ka = 1.6 × 10 −10 , pKa = −log(1.6 × 10 −10 ) = 9.80
Kw 1.0 × 10 −14
C5H5NH+, Ka = = = 5.9 × 10 −6 , pKa = 5.23
K b , C5 H 5 N 1.7 × 10 −9
From the pKa values, the correct ordering at the halfway point to equivalence would be i
< iii < iv < ii. Note that for the weak base-strong acid titration using C5H5N, the pH is acidic
at the halfway point to equivalence, whereas the weak acid-strong base titration using
HOC6H5 is basic at the halfway point to equivalence. This is fine; this will always happen
when the weak base titrated has a Kb < 1 × 10 −7 (so Ka of the conjugate acid is greater than
1 × 10−7) and when the weak acid titrated has a Ka < 1 × 10 −7 (so Kb of the conjugate base
is greater than 1 × 10−7).
60. HA + OH− → A− + H2O; it takes 25.0 mL of 0.100 M NaOH to reach the equivalence
point where mmol HA = mmol OH− = 25.0 mL(0.100 M) = 2.50 mmol. At the equivalence
point, some HCl is added. The H+ from the strong acid reacts to completion with the best base
present, A−.
H+ + A− → HA
Before 13.0 mL × 0.100 M 2.5 mmol 0
Change −1.3 mmol −1.3 mmol +1.3 mmol
After 0 1.2 mmol 1.3 mmol
A buffer solution is present after the H+ has reacted completely.

[A − ]  1.2 mmol / VT 
pH = pKa + log , 4.7 = pKa + log  
[HA]  1.3 mmol / VT 
Because the log term will be negative [log(1.2/1.3) = −0.035)], the pKa value of the acid must
be greater than 4.7.
61. a. Because all acids are the same initial concentration, the pH curve with the highest pH at 0
mL of NaOH added will correspond to the titration of the weakest acid. This is curve f.
b. The pH curve with the lowest pH at 0 mL of NaOH added will correspond to the titration
of the strongest acid. This is pH curve a.
The best point to look at to differentiate a strong acid from a weak acid titration (if initial
concentrations are not known) is the equivalence point pH. If the pH = 7.00, the acid
titrated is a strong acid; if the pH is greater than 7.00, the acid titrated is a weak acid.
c. For a weak acid-strong base titration, the pH at the halfway point to equivalence is equal
to the pKa value. The pH curve, which represents the titration of an acid with Ka = 1.0 ×
10−6, will have a pH = −log(1 × 10−6) = 6.0 at the halfway point. The equivalence point,
from the plots, occurs at 50 mL NaOH added, so the halfway point is 25 mL. Plot d has a
pH ≈ 6.0 at 25 mL of NaOH added, so the acid titrated in this pH curve (plot d) has
Ka ≈ 1 × 10−6.
62. The three key points to emphasize in your sketch are the initial pH, the pH at the halfway point
to equivalence, and the pH at the equivalence point. For all the weak bases titrated, pH = pKa
at the halfway point to equivalence (50.0 mL HCl added) because [weak base] = [conjugate
acid] at this point. Here, the weak base with Kb = 1 × 10 −5 has a conjugate acid with Ka = 1 ×
10−9, so pH = 9.0 at the halfway point. The weak base with Kb = 1 × 10 −10 has a pH = 4.0 at
the halfway point to equivalence. For the initial pH, the strong base has the highest pH (most
basic), whereas the weakest base has the lowest pH (least basic). At the equivalence point
(100.0 mL HCl added), the strong base titration has pH = 7.0. The weak bases titrated have
acidic pH’s because the conjugate acids of the weak bases titrated are the major species present.
The weakest base has the strongest conjugate acid so its pH will be lowest (most acidic) at the
equivalence point.
strong base
pH 7.0 Kb = 10-5
Kb = 10-10
Volume HCl added (mL)
63. This is a strong acid (HClO4) titrated by a strong base (KOH). Added OH− from the strong
base will react completely with the H+ present from the strong acid to produce H2O.
a. Only strong acid present. [H+] = 0.200 M; pH = 0.699

0.100 mmol OH −
b. mmol OH− added = 10.0 mL × = 1.00 mmol OH-
mL
0.200 mmol H +
mmol H+ present = 40.0 mL × = 8.0 mmol H+
mL
Note: The units millimoles are usually easier numbers to work with. The units for
molarity are moles per liter but are also equal to millimoles per milliliter.
H+ + OH− → H2O
Before 8.00 mmol 1.00 mmol
Change −1.00 mmol −1.00 mmol Reacts completely
After 7.00 mmol 0
7.00 mmol H +
The excess H+ determines the pH. [H+]excess = = 0.140 M
40.0 mL + 10.0 mL
pH = −log(0.140) = 0.854
c. mmol OH− added = 40.0 mL × 0.100 M = 4.00 mmol OH−
H+ + OH− → H2O
After 4.00 mmol 0
4.00 mmol
[H+]excess = = 0.0500 M; pH = 1.301
(40.0 + 40.0) mL
d. mmol OH- added = 80.0 mL × 0.100 M = 8.00 mmol OH−; this is the equivalence point
because we have added just enough OH- to react with all the acid present. For a strong
acid-strong base titration, pH = 7.00 at the equivalence point because only neutral species
are present (K+, ClO4−, H2O).
e. mmol OH− added = 100.0 mL × 0.100 M = 10.0 mmol OH−

H+ + OH− → H2O
After 0 2.0 mmol
Past the equivalence point, the pH is determined by the excess OH- present.
2.0 mmol
[OH−]excess = = 0.014 M; pOH = 1.85; pH = 12.15
(40.0 + 100.0) mL
64. This is a strong base, Ba(OH)2, titrated by a strong acid, HCl. The added strong acid will
neutralize the OH− from the strong base. As is always the case when a strong acid and/or
strong base reacts, the reaction is assumed to go to completion.
a. Only a strong base is present, but it breaks up into two moles of OH− ions for every mole
of Ba(OH)2. [OH−] = 2 × 0.100 M = 0.200 M; pOH = 0.699; pH = 13.301
0.100 mmol Ba (OH) 2 2 mmol OH −
b. mmol OH− present = 80.0 mL × ×
mL mmol Ba (OH) 2
= 16.0 mmol OH−
0.400 mmol H +
mmol H+ added = 20.0 mL × = 8.00 mmol H+
mL
OH− + H+ → H2O
After 8.0 mmol 0
8.0 mmol OH −
[OH−]excess = = 0.080 M; pOH = 1.10; pH = 12.90
80.0 mL + 20.0 mL
c. mmol H+ added = 30.0 mL × 0.400 M = 12.0 mmol H+
OH− + H+ → H2O
After 4.0 mmol 0
4.0 mmol OH −
[OH−]excess = = 0.036 M; pOH = 1.44; pH = 12.56
(80.0 + 30.0) mL
d. mmol H+ added = 40.0 mL × 0.400 M = 16.0 mmol H+; this is the equivalence point.
Because the H+ will exactly neutralize the OH− from the strong base, all we have in
solution is Ba2+, Cl−, and H2O. All are neutral species, so pH = 7.00.
e. mmol H+ added = 80.0 mL × 0.400 M = 32.0 mmol H+
OH− + H+ → H2O
After 0 16.0 mmol
16.0 mmol H +
[H+]excess = = 0.100 M; pH = 1.000
(80.0 + 80.0) mL
65. This is a weak acid (HC2H3O2) titrated by a strong base (KOH).
a. Only weak acid is present. Solving the weak acid problem:
HC2H3O2 ⇌ H+ + C2H3O2−
x mol/L HC2H3O2 dissociates to reach equilibrium
x2 x2
Ka = 1.8 × 10−5 = ≈ , x = [H+] = 1.9 × 10−3 M
0.200 − x 0.200
pH = 2.72; assumptions good.
b. The added OH− will react completely with the best acid present, HC2H3O2.
0.200 mmol HC 2 H 3O 2
mmol HC2H3O2 present = 100.0 mL × = 20.0 mmol HC2H3O2
mL
0.100 mmol OH −
mmol OH− added = 50.0 mL × = 5.00 mmol OH−
mL
HC2H3O2 + OH− → C2H3O2− + H2O

Before 20.0 mmol 5.00 mmol 0
Change −5.00 mmol −5.00 mmol → +5.00 mmol Reacts completely
After 15.0 mmol 0 5.00 mmol
After reaction of all the strong base, we have a buffer solution containing a weak acid
(HC2H3O2) and its conjugate base (C2H3O2−). We will use the Henderson-Hasselbalch
equation to solve for the pH. Let VT = total volume:
−
[C 2 H 3 O 2 ]  5.00 mmol/VT 
pH = pKa + log = −log (1.8 × 10−5) + log  ,
[HC 2 H 3O 2 ]  15.0 mmol/VT 
 5.00 
pH = 4.74 + log   = 4.74 + (-0.477) = 4.26
 15.0 
Note that the total volume cancels in the Henderson-Hasselbalch equation. For the
[base]/[acid] term, the mole ratio equals the concentration ratio because the components of
the buffer are always in the same volume of solution.
c. mmol OH− added = 100.0 mL × (0.100 mmol OH−/mL) = 10.0 mmol OH−; the same
amount (20.0 mmol) of HC2H3O2 is present as before (it doesn’t change). As before, let
the OH− react to completion, then see what is remaining in solution after this reaction.
HC2H3O2 + OH− → C2H3O2− + H2O

A buffer solution results after reaction. Because [C2H3O2−] = [HC2H3O2] = 10.0 mmol/total
volume, pH = pKa. This is always true at the halfway point to equivalence for a weak acid-
strong base titration, pH = pKa.
pH = −log(1.8 × 10−5) = 4.74
d. mmol OH− added = 150.0 mL × 0.100 M = 15.0 mmol OH−. Added OH− reacts
completely with the weak acid.
HC2H3O2 + OH− → C2H3O2− + H2O

We have a buffer solution after all the OH− reacts to completion. Using the Henderson-
−
[C 2 H 3 O 2 ]  15.0 mmol 
pH = 4.74 + log = 4.74 + log  
[HC 2 H 3O 2 ]  5.0 mmol 
pH = 4.74 + 0.48 = 5.22
e. mmol OH− added = 200.00 mL × 0.100 M = 20.0 mmol OH−; as before, let the added OH−
react to completion with the weak acid; then see what is in solution after this reaction.
HC2H3O2 + OH− → C2H3O2− + H2O

After 0 0 20.0 mmol
This is the equivalence point. Enough OH− has been added to exactly neutralize all the
weak acid present initially. All that remains that affects the pH at the equivalence point is
the conjugate base of the weak acid (C2H3O2−). This is a weak base equilibrium problem.
1.0 × 10 −14
C2H3O2− + H2O ⇌ HC2H3O2 + OH−
Kw
=Kb =
Kb 1.8 × 10 −5
Initial 20.0 mmol/300.0 mL 0 0 Kb = 5.6 × 10−9
-
x mol/L C2H3O2 reacts with H2O to reach equilibrium
Equil. 0.0667 − x x x
x2 x2
Kb = 5.6 × 10−10 = ≈ , x = [OH−] = 6.1 × 10−6 M
0.0667 − x 0.0667
pOH = 5.21; pH = 8.79; assumptions good.
f. mmol OH− added = 250.0 mL × 0.100 M = 25.0 mmol OH−
HC2H3O2 + OH− → C2H3O2− + H2O

After the titration reaction, we have a solution containing excess OH− and a weak base
C2H3O2−. When a strong base and a weak base are both present, assume that the amount
of OH− added from the weak base will be minimal; that is, the pH past the equivalence
point is determined by the amount of excess strong base.
5.0 mmol
[OH−]excess = = 0.014 M; pOH = 1.85; pH = 12.15
100.0 mL + 250.0 mL
66. This is a weak base (H2NNH2) titrated by a strong acid (HNO3). To calculate the pH at the
various points, let the strong acid react completely with the weak base present; then see what
is in solution.
a. Only a weak base is present. Solve the weak base equilibrium problem.
H2NNH2 + H2O ⇌ H2NNH3+ + OH−

Equil. 0.100 - x x x
x2 x2
Kb = 3.0 × 10−6 = ≈ , x = [OH−] = 5.5 × 10−4 M
0.100 − x 0.100
0.100 mmol H 2 NNH 2
b. mmol H2NNH2 present = 100.0 mL × = 10.0 mmol H2NNH2
mL
0.200 mmol H +
mL
H2NNH2 + H+ → H2NNH3+
A buffer solution results after the titration reaction. Solving using the Henderson-
[base] K 1.0 × 10 −14
pH = pKa + log ; Ka = w = = 3.3 × 10−9
[acid] Kb 3.0 × 10 −6
 6.0 mmol / VT 
pH = −log(3.3 × 10−9) + log  , where VT (= total volume) cancels.
 4.00 mmol / VT 
pH = 8.48 + log(1.5) = 8.48 + 0.18 = 8.66
This is the halfway point to equivalence where [H2NNH3+] = [H2NNH2]. At this point,
pH = pKa (which is characteristic of the halfway point for any weak base-strong acid
titration).
pH = −log(3.3 × 10−9) = 8.48

d. mmol H+ added = 40.0 mL × 0.200 M = 8.00 mmol H+
A buffer solution results.
[base]  2.0 mmol / VT 

pH = pKa + log = 8.48 + log   = 8.48 + (−0.60) = 7.88
[acid]  8.00 mmol / VT 
After 0 0 10.0 mmol
As is always the case in a weak base-strong acid titration, the pH at the equivalence point
is acidic because only a weak acid (H2NNH3+) is present. Solving the weak acid
equilibrium problem:
H2NNH3+ ⇌ H+ + H2NNH2
Initial 10.0 mmol/150.0 mL 0 0
Equil. 0.0667 − x x x
x2 x2
Ka = 3.3 × 10−9 = ≈ , x = [H+] = 1.5 × 10−5 M
0.0667 − x 0.0667
f. mmol H+ added = 100.0 mL × 0.200 M = 20.0 mmol H+
Two acids are present past the equivalence point, but the excess H+ will determine the pH
of the solution since H2NNH3+ is a weak acid.
10.0 mmol
[H+]excess = = 0.0500 M; pH = 1.301
100.0 mL + 100.0 mL
67. We will do sample calculations for the various parts of the titration. All results are
summarized in Table 8.1 at the end of Exercise 70.
At the beginning of the titration, only the weak acid HC3H5O3 is present. Let HLac =
HC3H5O3 and Lac− = C3H5O3−.
HLac ⇌ H+ + Lac− Ka = 10−3.86 = 1.4 × 10−4

x mol/L HLac dissociates to reach equilibrium
x2 x2
1.4 × 10−4 = ≈ , x = [H+] = 3.7 × 10−3 M; pH = 2.43; assumptions good.
0.100 − x 0.100
Up to the stoichiometric point, we calculate the pH using the Henderson-Hasselbalch
equation. This is the buffer region. For example, at 4.0 mL of NaOH added:
0.100 mmol
initial mmol HLac present = 25.0 mL × = 2.50 mmol HLac
mL
0.100 mmol
mL
Note: The units millimoles are usually easier numbers to work with. The units for molarity
are moles per liter but are also equal to millimoles per milliliter.
The 0.40 mmol of added OH− converts 0.40 mmol HLac to 0.40 mmol Lac− according to the
equation:
HLac + OH− → Lac− + H2O Reacts completely since a strong base is added.
mmol HLac remaining = 2.50 − 0.40 = 2.10 mmol; mmol Lac− produced = 0.40 mmol
We have a buffer solution. Using the Henderson-Hasselbalch equation where pKa = 3.86:
[Lac − ] (0.40)
pH = pKa + log = 3.86 + log
[HLac] (2.10)
Note: the total volume cancels, so we can use the ratio of moles or millimoles.
pH = 3.86 − 0.72 = 3.14
Other points in the buffer region are calculated in a similar fashion. Perform a stoichiometry
problem first, followed by a buffer problem. The buffer region includes all points up to and
including 24.9 mL OH− added.
At the stoichiometric point (25.0 mL OH− added), we have added enough OH−to convert all
of the HLac (2.50 mmol) into its conjugate base (Lac−). All that is present is a weak base.
To determine the pH, we perform a weak base calculation.
2.50 mmol
[Lac−]0 = = 0.0500 M
25.0 mL + 25.0 mL
1.0 × 10 −14
Lac− + H2O ⇌ HLac + OH− Kb = = 7.1 × 10−11
1.4 × 10 − 4
Initial 0.0500 M 0 0
−
x mol/L Lac reacts with H2O to reach equilibrium
Equil. 0.0500 − x x x
x2 x2
Kb = ≈ = 7.1 × 10−11
0.0500 − x 0.0500
Past the stoichiometric point, we have added more than 2.50 mmol of NaOH. The pH will be
determined by the excess OH− ion present. An example of this calculation follows.
0.100 mmol
At 25.1 mL: OH− added = 25.1 mL × = 2.51 mmol OH−
mL
2.50 mmol OH− neutralizes all the weak acid present. The remainder is excess OH−.
Excess OH− = 2.51 − 2.50 = 0.01 mmol OH−

0.01 mmol
[OH−]excess = = 2 × 10−4 M; pOH = 3.7; pH = 10.3
(25.0 + 25.1) mL
All results are listed in Table 8.1 at the end of the solution to Exercise 70.
68. Results for all points are summarized in Table 8.1 at the end of the solution to Exercise 70. At
the beginning of the titration, we have a weak acid problem:
HOPr ⇌ H+ + OPr- HOPr = HC3H5O2

Initial 0.100 M ~0 0 OPr- = C3H5O2−
x mol/L HOPr acid dissociates to reach equilibrium
[H + ][OPr − ] x2 x2
Ka = = 1.3 × 10−5 = ≈
[HOPr] 0.100 − x 0.100
x = [H+] = 1.1 × 10−3 M; pH = 2.96; assumptions good.
The buffer region is from 4.0 to 24.9 mL of OH− added. We will do a sample calculation at
24.0 mL OH− added.
0.100 mmol
Initial mmol HOPr present = 25.0 mL × = 2.50 mmol HOPr
mL
0.100 mmol
mL
The added strong base converts HOPr into OPr−.
HOPr + OH− → OPr- + H2O

A buffer solution results. Using the Henderson-Hasselbalch equation where pKa =

−log(1.3 × 10−5) = 4.89:
[base] [OPr − ]
pH = pKa + log = 4.89 + log
[acid] [HOPr]
 2.40 
pH = 4.89 + log   = 4.89 + 1.38 = 6.27 (Volume cancels, so we can use the
 0.10 
millimole ratio in the log term.)
All points in the buffer region 4.0 mL to 24.9 mL are calculated this way. See Table 8.1 at
the end of Exercise 70 for all the results.
At the stoichiometric point (25.0 mL KOH added), only a weak base (OPr−) is present:
OPr- + H2O ⇌ OH− + HOPr

2.50 mmol
Initial = 0.0500 M 0 0
50.0 mL
x mol/L OPr− reacts with H2O to reach equilibrium
Equil. 0.0500 − x x x
[OH − ][HOPr] Kw x2 x2
Kb = = = 7.7 Η 10−10
= ≈
[OPr − ] Ka 0.0500 − x 0.0500
x = 6.2 × 10−6 M = [OH−], pOH = 5.21, pH = 8.79; assumptions good.
Beyond the stoichiometric point, the pH is determined by the excess strong base added. The
results are the same as those in Exercise 67 (see Table 8.1).
For example at 26.0 mL KOH added:

2.60 mmol − 2.50 mmol
[OH−] = = 2.0 × 10−3 M; pOH = 2.70; pH = 11.30
(25.0 + 26.0) mL
69. At beginning of the titration, only the weak base NH3 is present. As always, solve for the pH
using the Kb reaction for NH3.
NH3 + H2O ⇌ NH4+ + OH− Kb = 1.8 × 10−5

x2 x2
Kb = ≈ = 1.8 × 10−5
0.100 − x 0.100
In the buffer region (4.0 − 24.9 mL), we can use the Henderson-Hasselbalch equation:
1.0 × 10 −14 [ NH 3 ]
Ka = −5
= 5.6 × 10−10; pKa = 9.25; pH = 9.25 + log +
1.8 × 10 [ NH 4 ]
We must determine the amounts of NH3 and NH4+ present after the added H+ reacts
completely with the NH3. For example, after 8.0 mL HCl added:
0.100 mmol
initial mmol NH3 present = 25.0 mL × = 2.50 mmol NH3
mL
0.100 mmol
mL
Added H+ reacts with NH3 to completion: NH3 + H+ → NH4+
mmol NH3 remaining = 2.50 − 0.80 = 1.70 mmol; mmol NH4+ produced = 0.80 mmol
1.70
pH = 9.25 + log = 9.58 (Mole ratios can be used since the total volume cancels.)
0.80
Other points in the buffer region are calculated in similar fashion. Results are summarized in
Table 8.1 at the end of Exercise 70.
At the stoichiometric point (25.0 mL H+ added), just enough HCl has been added to convert
all the weak base (NH3) into its conjugate acid (NH4+). Perform a weak acid calculation.
[NH4+]0 = 2.50 mmol/50.0 mL = 0.0500 M
NH4+ ⇌ H+ + NH3 Ka = 5.6 × 10−10

Equil. 0.0500 - x x x
x2 x2
5.6 × 10−10 = ≈ , x = [H+] = 5.3 × 10−6 M; pH = 5.28
0.0500 − x 0.0500
Assumptions good.
Beyond the stoichiometric point, the pH is determined by the excess H+. For example, at 28.0
mL of H+ added:
0.100 mmol
H+ added = 28.0 mL × = 2.80 mmol H+
mL
Excess H+ = 2.80 mmol − 2.50 mmol = 0.30 mmol excess H+
0.30 mmol
[H+]excess = = 5.7 × 10−3 M; pH = 2.24
(25.0 + 28.0) mL
All results are summarized in Table 8.1 at the end of Exercise 70.
70. Initially, a weak base problem:
py + H2O ⇌ Hpy+ + OH− py is pyridine.
[Hpy + ][OH − ] x2 x2
Kb = = ≈ ≈ 1.7 × 10−9
[py] 0.100 − x 0.100
Buffer region (4.0 − 24.5 mL): Added H+ reacts completely with py: py + H+ → Hpy+.
Determine the moles (or millimoles) of py and Hpy+ after reaction, then use the Henderson-
Hasselbalch equation to solve for the pH.
Kw 1.0 × 10 −14 [py]
Ka = = = 5.9 × 10−6; pKa = 5.23; pH = 5.23 + log
Kb 1.7 × 10 −9
[Hpy + ]
Results in the buffer region are summarized in Table 8.1, which follows this problem. See
Exercise 69 for a similar sample calculation.
At the stoichiometric point (25.0 mL H+ added), this is a weak acid problem since just enough
H+ has been added to convert all the weak base into its conjugate acid. The initial
concentration of [Hpy+] = 0.0500 M.
Hpy+ ⇌ py + H+ Ka = 5.9 × 10−6

Equil. 0.0500 − x x x
x2 x2
5.9 × 10−6 = ≈ , x = [H+] = 5.4 × 10−4 M; pH = 3.27
0.0500 − x 0.0500
Asumptions good.
Beyond the equivalence point, the pH determination is made by calculating the concentration
of excess H+. See Exercise 8.69 for an example. All results are summarized in Table 8.1 on
the next page.
Table 8.1 Summary of pH Results for Exercises 67 − 70 (Graph follows)
Titrant Exercise Exercise Exercise Exercise

mL 67 68 69 70___
0.0 2.43 2.96 11.11 9.11

4.0 3.14 4.17 9.97 5.95
8.0 3.53 4.56 9.58 5.56
12.5 3.86 4.89 9.25 5.23
20.0 4.46 5.49 8.65 4.63
24.0 5.24 6.27 7.87 3.85
24.5 5.6 6.6 7.6 3.5
24.9 6.3 7.3 6.9 -
25.0 8.28 8.79 5.28 3.27
25.1 10.3 10.3 3.7 -
26.0 11.30 11.30 2.71 2.71
28.0 11.75 11.75 2.24 2.25
30.0 11.96 11.96 2.04 2.04
71. a. This is a weak acid-strong base titration. At the halfway point to equivalence, [weak
acid] = [conjugate base], so pH = pKa (always for a weak acid-strong base titration).
pH = −log(6.4 × 10−5) = 4.19
mmol HC7H5O2 present = 100.0 mL × 0.10 M = 10. mmol HC7H5O2. For the equivalence
point, 10. mmol of OH− must be added. The volume of OH− added to reach the
equivalence point is:
1 mL
10. mmol OH− × = 1.0 × 102 mL OH−
0.10 mmol OH −
At the equivalence point, 10. mmol of HC7H5O2 is neutralized by 10. mmol of OH− to
produce 10. mmol of C7H5O2−. This is a weak base. The total volume of the solution is
100.0 mL + 1.0 × 102 mL = 2.0 × 102 mL. Solving the weak base equilibrium problem:
1.0 × 10 −14
C7H5O2− + H2O ⇌ HC7H5O2 + OH− Kb = = 1.6 × 10−10
6.4 × 10 −5
Initial 10. mmol/2.0 × 102 mL 0 0
x2 x2
Kb = 1.6 × 10−10 = ≈ , x = [OH−] = 2.8 × 10−6 M
0.050 − x 0.050
b. At the halfway point to equivalence for a weak base-strong acid titration, pH = pKa
because [weak base] = [conjugate acid].
Kw 1.0 × 10 −14
Ka = = = 1.8 × 10−11; pH = pKa = −log(1.8 × 10−11) = 10.74
Kb 5.6 × 10 − 4
For the equivalence point (mmol acid added = mmol base present):
mmol C2H5NH2 present = 100.0 mL × 0.10 M = 10. mmol C2H5NH2

1 mL
mL H+ added = 10. mmol H+ × +
= 50. mL H+
0.20 mmol H
The strong acid added completely converts the weak base into its conjugate acid.
Therefore, at the equivalence point, [C2H5NH3+]0 = 10. mmol/(100.0 + 50.) mL = 0.067
M. Solving the weak acid equilibrium problem:
C2H5NH3+ ⇌ H+ + C2H5NH2
Initial 0.067 M 0 0
x2 x2
Ka = 1.8 × 10−11 = ≈ , x = [H+] = 1.1 × 10−6 M
0.067 − x 0.067
c. In a strong acid-strong base titration, the halfway point has no special significance other
than that exactly one-half of the original amount of acid present has been neutralized.
mmol H+ present = 100.0 mL × 0.50 M = 50. mmol H+

1 mL
mL OH− added = 25 mmol OH− × = 1.0 × 102 mL OH−
0.25 mmol
H+ + OH− → H2O
Before 50. mmol 25 mmol
After 25 mmol 0
25 mmol
[H+]excess = = 0.13 M; pH = 0.89
(100.0 + 1.0 × 10 2 ) mL
At the equivalence point of a strong acid-strong base titration, only neutral species are
present (Na+, Cl−, and H2O), so the pH = 7.00.
0.10 mmol 0.10 mmol

72. 75.0 mL × = 7.5 mmol HA; 30.0 mL × = 3.0 mmol OH− added
mL mL
The added strong base reacts to completion with the weak acid to form the conjugate base of
the weak acid and H2O.
HA + OH− → A− + H2O
A buffer results after the OH− reacts to completion. Using the Henderson-Hasselbalch
equation:
[A − ]  3.0 mmol / 105.0 mmol 
pH = pKa + log , 5.50 = pKa + log  
[HA]  4.5 mmol / 105.0 mmol 
pKa = 5.50 − log(3.0/4.5) = 5.50 – (−0.18) = 5.68; Ka = 10 −5.68 = 2.1 × 10 −6
73. Mol H+ added = 0.0400 L × 0.100 mol/L = 0.00400 mol H+
The added strong acid reacts to completion with the weak base to form the conjugate acid of
the weak base and H2O. Let B = weak base:
B + H+ → BH+
Before 0.0100 mol 0.00400 mol 0
After 0.0060 0 0.0400 mol
After the H+ reacts to completion, we have a buffer solution. Using the Henderson-Hasselbalch
equation where VT = total volume:
[base] (0.0060/VT )
pH = pKa + log , 8.00 = pKa + log
[acid] (0.00400/VT )
(0.0060)
pKa = 8.00 − log = 8.00 – 0.18, pKa = 7.82
(0.00400)
For a conjugate acid-base pair, pKa + pKb = 14,00, so:
pKb = 14.00 – 7.82 = 6.18; Kb = 10 −6.18 = 6.6 × 10 −7

Indicators
74. An acid-base indicator marks the end point of a titration by changing color. Acid-base
indicators are weak acids themselves. We abbreviate the acid form of an indicator as HIn and
the conjugate base form as In−. The reason there is a color change with indicators is that the
HIn form has one color associated with it, whereas the In− form has a different color associated
with it. Which form dominates in solution and dictates the color is determined by the pH of the
solution. The related quilibrium is HIn ⇌ H+ + In−. In a very acidic solution, there are lots
of H+ ions present, which drives the indicator equilibrium to the left. The HIn form dominates,
and the color of the solution is the color due to the HIn form. In a very basic solution, H+ has
been removed from solution. This drives the indicator equilibrium to the right, and the In− form
dominates. In very basic solutions, the solution takes on the color of the In− form. In between
very acidic and very basic solutions, there is a range of pH values where the solution has
significant amounts of both the HIn and In− forms present. This is where the color change
occurs, and we want this pH to be close to the stoichiometric point of the titration. The pH at
which the color change occurs is determined by the Ka of the indicator.
Equivalence point: when enough titrant has been added to react exactly with the substance in
the solution being titrated. Endpoint: when the indicator changes color. We want the indicator
to tell us when we have reached the equivalence point. We can detect the endpoint visually and
assume that it is the equivalence point for doing stoichiometric calculations. They don’t have
to be as close as 0.01 pH units since, at the equivalence point, the pH is changing very rapidly
with added titrant. The range over which an indicator changes color only needs to be close to
the pH of the equivalence point.
The two forms of an indicator are different colors. The HIn form has one color and the In− form
has another color. To see only one color, that form must be in an approximately tenfold excess
or greater over the other form. When the ratio of the two forms is less than 10, both colors are
present. To go from [HIn]/[In−] = 10 to [HIn]/[In−] = 0.1 requires a change of 2 pH units (a
100-fold decrease in [H+]) as the indicator changes from the HIn color to the In− color.
From Figure 8.8, thymol blue has three colors associated with it: orange, yellow, and blue. In
order for this to happen, thymol blue must be a diprotic acid. The H2In form has the orange
color, the HIn− form has the yellow color, and the In2− form has the blue color associated with
it. Thymol blue cannot be monoprotic; monoprotic indicators only have two colors associated
with them (either the HIn color or the In− color).
[In − ][H + ]
75. HIn ⇌ In− + H+ Ka = = 1.0 × 10 −9
[HIn]
a. In a very acid solution, the HIn form dominates, so the solution will be yellow.
b. The color change occurs when the concentration of the more dominant form is
approximately ten times as great as the less dominant form of the indicator.
[HIn] 10 1
−
= ; Ka = 1.0 × 10 −9 =   [H+], [H+] = 1 × 10 −8 M
[In ] 1  10 
pH = 8.0 at color change change
c. This is way past the equivalence point (100.0 mL OH− added), so the solution is very
basic and the In− form of the indicator dominates. The solution will be blue.
[In − ][H + ]
76. HIn ⇌ In− + H+ Ka = = 10 −3.00 = 1.0 × 10−3
[HIn]
At 7.00% conversion of HIn into In−, [In−]/[HIn] = 7.00/93.00.
[In − ] 7.00
Ka = 1.0 × 10 −3 = × [H + ] = × [H + ], [H+] = 1.3 × 10 −2 M, pH = 1.89
[HIn] 93.00
The color of the base form will start to show when the pH is increased to 1.89.
77. pH > 5 for bromcresol green to be blue. pH < 8 for thymol blue to be yellow. The pH is
between 5 and 8.
78. a. yellow b. green (Both yellow and blue forms are present.)
c. yellow d. blue
79. When choosing an indicator, we want the color change of the indicator to occur approximately
at the pH of the equivalence point. Since the pH generally changes very rapidly at the
equivalence point, we don’t have to be exact. This is especially true for strong acid-strong base
titrations. The following are some indicators where the color change occurs at about the pH of
the equivalence point.
Exercise pH at Eq. Pt. Indicator
63 7.00 bromthymol blue or phenol red

65 8.79 o-cresolphthalein or phenolphthalein
80. Exercise pH at Eq. Pt. Indicator
64 7.00 bromthymol blue or phenol red

66 4.82 bromcresol green

69 5.28 bromcresol green

70 3.27 2,4-dinitrophenol
The titration in Exercise 70 will be very difficult to mark the equivalence point. The pH
break at the equivalence point is very small.
83. The color of the indicator will change over the approximate range of pH = pKa ± 1 = 5.3 ± 1.
Therefore, the useful pH range of methyl red where it changes color would be about 4.3 (red)
to 6.3 (yellow). Note that at pH < 4.3, the HIn form of the indicator dominates, and the color
of the solution is the color of HIn (red). At pH > 6.3, the In− form of the indicator dominates,
and the color of the solution is the color of In− (yellow). In titrating a weak acid with base, we
start off with an acidic solution with pH < 4.3, so the color would change from red to reddish
orange at pH ≈ 4.3. In titrating a weak base with acid, the color change would be from yellow
to yellowish orange at pH ≈ 6.3. Only a weak base-strong acid titration would have an acidic
pH at the equivalence point, so only in this type of titration would the color change of methyl
red indicate the approximate endpoint.
84. For bromcresol green, the resulting green color indicates that both HIn and In− are present in
significant amounts. This occurs when pH ≈ pKa of the indicator. From results of the
bromcresol green indicator, pH ≈ 5.0 ([H+] ≈ 1 × 10-5). Note that the results of the first two
indicators are inconclusive.
HX ⇌ H+ + X−; from the typical weak acid setup: [H+] = [X−] ≈ 1 × 10−5 M , [HX] ≈ 0.01 M
[H + ][X − ] (1 × 10 −5 ) 2
Ka = = = 1 × 10−8
[HX] 0.01
Polyprotic Acid Titrations
85. The first titration plot (from 0 − 100.0 mL) corresponds to the titration of H2A by OH−. The
reaction is H2A + OH− → HA− + H2O. After all the H2A has been reacted, the second titration
(from 100.0 – 200.0 mL) corresponds to the titration of HA− by OH−. The reaction is HA− +
OH− → A2− + H2O.
a. At 100.0 mL of NaOH, just enough OH− has been added to react completely with all of
the H2A present (mol OH− added = mol H2A present initially). From the balanced equa-
tion, the mol of HA− produced will equal the mol of H2A present initially. Because mol of
HA− present at 100.0 mL OH− added equals the mol of H2A present initially, exactly 100.0
mL more of NaOH must be added to react with all of the HA−. The volume of NaOH added
to reach the second equivalence point equals 100.0 mL + 100.0 mL = 200.0 mL.
b. H2A + OH− → HA− + H2O is the reaction occurring from 0 − 100.0 mL NaOH added.
i. No reaction has taken place, so H2A and H2O are the major species.
ii. Adding OH− converts H2A into HA−. The major species between 0 mL and 100.0
mL NaOH added are H2A, HA−, H2O, and Na+.
iii. At 100.0 mL NaOH added, mol of OH− = mol H2A, so all of the H2A present
initially has been converted into HA−. The major species are HA−, H2O, and Na+.
iv. Between 100.0 and 200.0 mL NaOH added, the OH− converts HA− into A2−. The
major species are HA−, A2− , H2O, and Na+.
v. At the second equivalence point (200.0 mL), just enough OH− has been added to
convert all of the HA− into A2−. The major species are A2−, H2O, and Na+.
vi. Past 200.0 mL NaOH added, excess OH− is present. The major species are OH−,
A2−, H2O, and Na+.
c. 50.0 mL of NaOH added corresponds to the first halfway point to equivalence. Exactly
one-half of the H2A present initially has been converted into its conjugate base HA−, so
[H2A] = [HA−] in this buffer solution.
[HA − ][H + ]
H2A ⇌ HA− + H+ Ka =
1 [H 2 A]
When [HA−] = [H2A], then K a = [H+] or pK a = pH.

1 1
Here, pH = 4.0, so pK a = 4.0 and K a = 10 −4.0 = 1 × 10 −4 .

1 1
150.0 mL of NaOH added correspond to the second halfway point to equivalence, where
[HA−] = [A2−] in this buffer solution.
[A 2− ][H + ]
HA− ⇌ A2− + H+ Ka =
2
[HA − ]
When [A2−] = [HA−], then K a = [H+] or pK a = pH.

2 2
Here, pH = 8.0, so pK a = 8.0 and K a = 10-8.0 = 1 × 10 −8 .

2 2
86. 50.0 mL × (0.10 mmol H2A/mL) = 5.0 mmol H2A initially
To reach the first equivalence point, 5.0 mmol OH− must be added. This occurs after addition
of 50.0 mL of 0.10 M NaOH. At the first equivalence point for a diprotic acid, pH = ( pK a1 +
pK a 2 )/2 = 8.00. Addition of 25.0 mL of 0.10 M NaOH will be the first halfway point to
equivalence, where [H2A] = [HA−] and pH = pK a1 = 6.70. Solving for the Ka values:
pK a1 = 6.70, K a1 = 10−6.70 = 2.0 × 10−7
pK a1 + pK a 2 6.70 + pK a 2
= 8.00, = 8.00, pK a 2 = 9.30, K a 2 = 10−9.30 = 5.0 × 10−10
2 2
87. 100.0 mL × 0.0500 M = 5.00 mmol H3X initially
a. Because K a1 >> K a 2 >> K a 3 , pH initially is determined by H3X equilibrium reaction.
H3X ⇌ H+ + H2X−
Initial 0.0500 M ~0 0
Equil. 0.0500 − x x x
x2 x2
K a1 = 1.0 × 10−3 = ≈ , x = 7.1 × 10−3; assumption poor.
0.0500 − x 0.0500
Using the quadratic formula:
x2 + (1.0 × 10−3)x − 5.0 × 10−5 = 0, x = 6.6 × 10−3 M = [H+]; pH = 2.18
b. 1.00 mmol OH− added converts H3X into H2X−. After this reaction goes to completion,
4.00 mmol H3X and 1.00 mmol H2X− are in a total volume of 110.0 mL. Solving the
buffer problem:
H3X ⇌ H+ + H2X−
Initial 0.0364 M ~0 0.00909 M
Equil. 0.0364 − x x 0.00909 + x
x(0.00909 + x)
K a1 = 1.0 × 10−3 = ; assumption that x is small does not work here.
0.0364 − x
Using the quadratic formula and carrying extra significant figures:
x2 + (1.01 × 10−2)x − 3.64 × 10−5 = 0, x = 2.8 × 10−3 M = [H+]; pH = 2.55
c. 2.50 mmol OH− added results in 2.50 mmol H3X and 2.50 mmol H2X− after OH− reacts
completely with H3X. This is the first halfway point to equivalence. pH = p K a1 = 3.00;
assumptions good (5% error).
d. 5.00 mmol OH− added results in 5.00 mmol H2X− after OH− reacts completely with H3X.
This is the first stoichiometric point.
pK a1 + pK a 2 3.00 + 7.00
pH = = = 5.00
2 2
e. 6.00 mmol OH−added results in 4.00 mmol H2X− and 1.00 mmol HX2− after OH− reacts
completely with H3X and then reacts completely with H2X−.
Using the H2X− ⇌ H+ + HX2− reaction:

[HX 2− ]
pH = pK a 2 + log = 7.00 − log(1.00/4.00) = 6.40; assumptions good.
[H 2 X − ]
f. 7.50 mmol KOH added results in 2.50 mmol H2X− and 2.50 mmol HX2− after OH− reacts
completely. This is the second halfway point to equivalence.
pH = pK a 2 = 7.00; assumptions good.
g. 10.0 mmol OH− added results in 5.0 mmol HX2− after OH− reacts completely. This is the
second stoichiometric point.
pK a 2 + pK a 3 7.00 + 12.00
pH = = = 9.50
2 2
h. 12.5 mmol OH− added results in 2.5 mmol HX2− and 2.5 mmol X3− after OH− reacts
completely with H3X first, then H2X−, and finally HX2-. This is the third halfway point to
equivalence. Usually pH = pK a 3 but normal assumptions don't hold. We must solve for
the pH exactly.
[X3−] = [HX2−] = 2.5 mmol/225.0 mL = 1.1 × 10−2 M
X3− + H2O ⇌ HX2− + OH− Kb =

Kw
= 1.0 × 10−2
K a3
Initial 0.011 M 0.011 M 0
Equil. 0.011 − x 0.011 + x x
x(0.011 + x)
Kb = 1.0 × 10−2 = ; using the quadratic formula:
0.011 − x
x2 + (2.1 × 10−2)x − 1.1 × 10−4 = 0, x = 4.3 × 10−3 M = OH−; pH = 11.63
i. 15.0 mmol OH− added results in 5.0 mmol X3− after OH− reacts completely. This is the
third stoichiometric point.
X3− + H2O ⇌ HX2− + OH− Kb =

Kw
= 1.0 × 10−2
K a3
5.0 mmol
Initial = 0.020 M 0 0
250.0 mL
x2 x2
Kb = , 1.0 × 10−2 ≈ , x = 1.4 × 10−2; assumption poor.
0.020 − x 0.020
Using the quadratic formula: x2 + (1.0 × 10−2)x − 2.0 × 10−4 = 0
x = [OH−] = 1.0 × 10−2 M; pH = 12.00
j. 20.0 mmol OH− added results in 5.0 mmol X3− and 5.0 mmol OH− excess after OH−
reacts completely. Because Kb for X3− is fairly large for a weak base, we have to worry
about the OH− contribution from X3−.
[X3−] = [OH−] = 5.0 mmol/300.0 mL = 1.7 × 10−2 M
X3− + H2O ⇌ OH− + HX2−

Initial 1.7 × 10−2 M 1.7 × 10−2 M 0
Equil. 1.7 × 10−2 − x 1.7 × 10−2 + x x
(1.7 × 10 −2 + x) x
Kb = 1.0 × 10−2 =
(1.7 × 10 − 2 − x)
Using the quadratic formula: x2 + (2.7 × 10−2)x − 1.7 × 10−4 = 0, x = 5.3 × 10−3 M
[OH−] = (1.7 × 10−2) + x = (1.7 × 10−2) + (5.3 × 10−3) = 2.2 × 10−2 M; pH = 12.34
88. a. Because K a1 >> K a 2 >> K a13 , the initial pH is determined by H3A. Consider only the
first dissociation.
H3A ⇌ H+ + H2A−
[H + ][H 2 A − ] x2 x2
K a1 = = = 1.5 × 10−4 ≈ , x = 3.9 × 10−3
[H 3 A] 0.100 − x 0.100
[H+] = 3.9 × 10−3 M; pH = 2.41; assumptions good.
b. 10.0 mL × 1.00 M = 10.0 mmol NaOH. Began with 100.0 mL × 0.100 M = 10.0 mmol
H3A. Added OH− converts H3A into H2A−. This takes us to the first stoichiometric point
where the amphoteric H2A− is the major species present.
pK a1 + pK a 2 3.82 + 7.52
pH = = = 5.67
2 2
c. 25.0 mL × 1.00 M = 25.0 mmol NaOH added. After OH− reacts completely, the mixture
contains 5.0 mmol HA2− and 5.0 mmol A3−.
[H + ][A 3− ]
K a3 = 2−
; because [A3−] = [HA2−], [H+] = K a 3 ; pH = pK a 3 = 11.30
[HA ]
This is the third halfway point to equivalence; assumptions good.
0.200 g
89. = 1.212 × 10−3 mol = 1.212 mmol H3A (carrying extra sig. figs.)
165.0 g/mol
a. 10.50 mL × 0.0500 M = 0.525 mmol OH− added; H3A + OH− → H2A− + H2O;
1.212 − 0.525 = 0.687 mmol H3A remains after OH− reacts completely and 0.525 mmol
H2A− formed. Solving the buffer problem using the K a1 reaction gives:
 0.525 
(10 −3.73 ) + 10 −3.73 
K a1 =  60.50  = 1.5 × 10−4; pK = −log(1.5 × 10−4) = 3.82
a1
0.687 −3.73
− 10
60.50
pK a1 + pK a 2 3.82 + pK a 2
First stoichiometric point: pH = = 5.19 =
2 2
pK a 2 = 6.56; K a 2 = 10−6.56 = 2.8 × 10−7
pK a 2 + pK a 3 6.56 + pK a 3
Second stoichiometric point: pH = , 8.00 =
2 2
pK a 3 = 9.44; K a 3 = 10−9.44 = 3.6 × 10−10
b. 1.212 mmol H3A = 0.0500 M OH − × VOH − , VOH − = 24.2 mL; 24.2 mL of OH− are necessary
to reach the first stoichiometric point. It will require 60.5 mL to reach the third halfway
point to equivalence, where pH = pK a 3 = 9.44. The pH at 59.0 mL of NaOH added
should be a little lower than 9.44.
c. 59.0 mL of 0.0500 M OH− = 2.95 mmol OH− added
H3A + OH− → H2A− + H2O

After 0 1.74 1.212
H2A− + OH− → HA2− + H2O

Before 1.212 1.74 0
After 0 0.53 1.212
HA2− + OH− → A3− + H2O

Before 1.212 0.53 0
Use the K a 3 reaction to solve for the [H+] in this buffer solution and make the normal
assumptions.
 0.53 mmol  +
  [H ]
−10  109 mL 
K a 3 = 3.6 × 10 = , [H+] = 4.6 × 10−10 M; pH = 9.34
 0.68 mmol 
 
 109 mL 
Assumptions good.
90. 100.0 mL × 0.100 M = 10.0 mmol H3A initially
a. 100.0 mL × 0.0500 mmol/mL = 5.00 mmol OH− added
This is the first halfway point to equivalence, where [H3A] = [H2A−] and pH = pK a1 .
pH = −log(5.0 × 10− 4) = 3.30; assumptions good.
b. Since pK a 2 = 8.00, a buffer mixture of H2A− and HA2− can produce a pH = 8.67 solution.
[HA 2− ] [HA 2− ]
8.67 = 8.00 + log , = 10+0.67 = 4.7
[H 2 A − ] [H 2 A − ]
Both species are in the same volume, so the mole ratio also equals 4.7. Let n = mmol:
nHA 2−
= 4.7, nHA 2− = (4.7)nH − ; nHA 2− + nH − = 10.0 mmol (mole balance)
2A 2A
nH −
2A
(5.7)nH − = 10.0 mmol, nH − = 1.8 mmol; nHA 2− = 8.2 mmol

2A 2A
To reach this point, we must add a total of 18.2 mmol NaOH. 10.0 mmol OH− converts all
of the 10.0 mmol H3A into H2A-. The next 8.2 mmol OH− converts 8.2 mmol H2A- into
8.2 mmol HA2− , leaving 1.8 mmol H2A−.
18.2 mmol = 0.0500 M × V, V = 364 mL NaOH
Note: Normal buffer assumptions are good.
91. a. Na+ is present in all solutions. The added H+ from HCl reacts completely with CO32− to
convert it into HCO3−. After all CO32− is reacted (after point C, the first equivalence point),
H+ then reacts completely with the next best base present, HCO3−. Point E represents the
second equivalence point. The major species present at the various points after H+ reacts
completely follow.
A. CO32−, H2O, Na+ B. CO32−, HCO3−, H2O, Cl− , Na+
C. HCO3−, H2O, Cl−, Na+ D. HCO3−, CO2 (H2CO3), H2O, Cl−, Na+
E. CO2 (H2CO3), H2O, Cl−, Na+ F. H+ (excess), CO2 (H2CO3), H2O, Cl−, Na+
b. Point A (initially):
1.0 × 10 −14
CO32− + H2O ⇌ HCO3− + OH− K b , CO 2− =
Kw
=
3 Ka2 4.8 × 10 −11
Initial 0.100 M 0 ~0 Kb = 2.1 × 10−4
−
[HCO 3 ][OH − ] x2 x2
Kb = 2.1 × 10−4 = 2−
= ≈
[CO 3 ] 0.100 − x 0.100
x = 4.6 × 10−3 M = [OH−]; pH = 11.66; assumptions good.
Point B: The first halfway point where [CO32−] = [HCO3−].
pH = pK a 2 = −log(4.8 × 10−11) = 10.32; assumptions good.
Point C: First equivalence point (25.00 mL of 0.100 M HCl added). The amphoteric
HCO3− is the major acid-base species present.
pK a1 + pK a 2
pH = ; pK a1 = −log(4.3 × 10−7) = 6.37
2
6.37 + 10.32
pH = = 8.35
2
Point D: The second halfway point where [HCO3−] = [H2CO3].
pH = pK a1 = 6.37; assumptions good.
Point E: This is the second equivalence point, where all of the CO32− present initially
has been converted into H2CO3 by the added strong acid. 50.0 mL HCl added.
[H2CO3] = 2.50 mmol/75.0 mL = 0.0333 M
H2CO3 ⇌ H+ + HCO3− K a1 = 4.3 × 10−7
Equil. 0.0333 − x x x
x2 x2
K a1 = 4.3 × 10−7 = ≈
0.0333 − x 0.0333
92. a. HA− ⇌ H+ + A2- Ka = 1 × 10−8; when [HA−] = [A2−], pH = pK a 2 = 8.00.
The titration reaction is A2− + H+ → HA− (goes to completion). Begin with 100.0 mL ×
0.200 mmol/mL = 20.0 mmol A2−. We need to convert 10.0 mmol A2− into HA- by adding
10.0 mmol H+. This will produce a solution where [HA−] = [A2−] and pH = pK a 2 = 8.00.
10.0 mmol = 1.00 mmol/mL × V, V = 10.0 mL HCl
b. At the second stoichiometric point, all A2− is converted into H2A. This requires 40.0
mmol HCl, which is 40.0 mL of 1.00 M HCl.
20.0 mmol
[H2A]0 = = 0.143 M; because K a1 >> K a 2 , H2A is the major source of H+.
140.0 mL
H2A ⇌ H+ + HA−
Initial 0.143 M 0 0
x2 x2
K a1 = , 1.0 × 10−3 ≈ , x = 0.012 M; check assumptions:
0.143 − x 0.143
0.012
× 100 = 8.4%; can't neglect x. Using successive approximations:
0.143
x = 0.0115 (carrying extra sig. figs.); [H+] = 0.0115 M and pH = 1.94
Solubility Equilibria
93. MX(s) ⇌ Mn+(aq) + Xn−(aq) Ksp = [Mn+][Xn−]; the Ksp reaction always refers to a solid
breaking up into its ions. The representations all show 1 : 1 salts, i.e., the formula of the solid
contains 1 cation for every 1 anion (either +1 and −1, or +2 and −2, or +3 and −3). The solution
with the largest number of ions (largest [Mn+] and [Xn−]) will have the largest Ksp value. From
the representations, the second beaker has the largest number of ions present, so this salt has
the largest Ksp value. Conversely, the third beaker, with the fewest number of hydrated ions,
will have the smallest Ksp value.
94. Ksp values can only be compared directly to determine relative solubilities when the salts
produce the same number of ions (have the same stoichiometry). Here, Ag2S and CuS do not
produce the same number of ions when they dissolve, so each has a different mathematical
relationship between the Ksp value and the molar solubility. To determine which salt has the
larger molar solubility, you must do the actual calculations and compare the two molar
solubility values.
95. The obvious choice is that the metal ion reacts with PO43− and forms an insoluble phosphate
salt. The other possibility is due to the weak base properties of PO43− (PO43− is the conjugate
base of the weak acid HPO42−, so it is a weak base). Because PO43− is a weak base in water,
OH− ions are present at a fairly large concentration. Hence the other potential precipitate is the
metal ion reacting with OH− to form an insoluble hydroxide salt.
96. For the Ksp reaction of a salt dissolving into its respective ions, a common ion would be one of
the ions in the salt added from an outside source. When a common ion (a product in the Ksp
reaction) is present, the Ksp equilibrium shifts to the left, resulting in less of the salt dissolving
into its ions (solubility decreases).
97. In our setups, s = solubility in mol/L. Because solids do not appear in the Ksp expression, we
do not need to worry about their initial or equilibrium amounts.
a. Ag3PO4(s) ⇌ 3 Ag+(aq) + PO43−(aq)

Initial 0 0
s mol/L of Ag3PO4(s) dissolves to reach equilibrium
Change −s → +3s +s
Equil. 3s s
Ksp = 1.8 × 10−18 = [Ag+]3[PO43−] = (3s)3(s) = 27s4
27s4 = 1.8 × 10−18, s = (6.7 × 10−20)1/4 = 1.6 × 10−5 mol/L = molar solubility
1.6 × 10 −5 mol Ag 3 PO 4 418.7 g Ag 3 PO 4
× = 6.7 × 10−3 g/L
L mol Ag 3 PO 4
b. CaCO3(s) ⇌ Ca2+(aq) + CO32−(aq)

Initial s = solubility (mol/L) 0 0
Equil. s s
Ksp = 8.7 × 10−9 = [Ca2+][CO32−] = s2, s = 9.3 × 10−5 mol/L

9.3 × 10 −5 mol 100.1 g
× = 9.3 × 10−3 g/L
L mol
c. Hg2Cl2(s) ⇌ Hg22+(aq) + 2 Cl−(aq)

Equil. s 2s
Ksp = 1.1 × 10−18 = [Hg22+][Cl−]2 = (s)(2s)2 = 4s3, s = 6.5 × 10−7 mol/L

6.5 × 10 −7 mol 472.1 g
× = 3.1 × 10−4 g/L
L mol
98. a. PbI2(s) ⇌ Pb2+(aq) + 2 I−(aq)

Equil. s 2s
Ksp = 1.4 × 10−8 = [Pb2+][I−]2 = s(2s)2 = 4s3
s = (1.4 × 10−8/4)1/3 = 1.5 × 10−3 mol/L = molar solubility
b. CdCO3(s) ⇌ Cd2+(aq) + CO32−(aq)

Equil. s s
Ksp = 5.2 × 10−12 = [Cd2+][CO32−] = s2, s = 2.3 × 10−6 mol/L
c. Sr3(PO4)2(s) ⇌ 3 Sr2+(aq) + 2 PO43−(aq)

Equil. 3s 2s
Ksp = 1 × 10−31 = [Sr2+]3[PO43−]2 = (3s)3(2s)2 = 108s5, s = 2 × 10−7 mol/L
99. In our setup, s = solubility of the ionic solid in mol/L. This is defined as the maximum amount
of a salt that can dissolve. Because solids do not appear in the Ksp expression, we do not need
to worry about their initial and equilibrium amounts.
a. CaC2O4(s) ⇌ Ca2+(aq) + C2O42−(aq)

Initial 0 0
s mol/L of CaC2O4(s) dissolves to reach equilibrium
Change −s → +s +s
Equil. s s
6.1 × 10 −3 g 1 mol CaC 2 O 4
From the problem, s = × = 4.8 × 10 −5 mol/L.
L 128.10 g
Ksp = [Ca2+][C2O42−] = (s)(s) = s2, Ksp = (4.8 × 10 −5 )2 = 2.3 × 10 −9
b. BiI3(s) ⇌ Bi3+(aq) + 3 I−(aq)

Initial 0 0
s mol/L of BiI3(s) dissolves to reach equilibrium
Change −s → +s +3s
Equil. s 3s
Ksp = [Bi3+][I−]3 = (s)(3s)3 = 27s4, Ksp = 27(1.32 × 10 −5 )4 = 8.20 × 10 −19
100. PbBr2(s) ⇌ Pb2+(aq) + 2 Br-(aq)

Initial 0 0
s mol/L of PbBr2(s) dissolves to reach equilibrium
Equil. s 2s
From the problem, s = [Pb2+] = 2.14 × 10 −2 M. So:
Ksp = [Pb2+][Br−]2 = s(2s)2 = 4s3, Ksp = 4(2.14 × 10 −2 )3 = 3.92 × 10 −5
101. Ag2C2O4(s) ⇌ 2 Ag+(aq) + C2O42−(aq)

Equil. 2s s
From the problem: [Ag+] = 2s = 2.2 × 10 −4 M, s = 1.1 × 10 −4 M
Ksp = [Ag+]2[C2O42−] = (2s)2(s) = 4s3 = 4(1.1 × 10 −4 )3 = 5.3 × 10 −12
102. M2X3(s) ⇌ 2 M3+(aq) + 3 X2−(aq) Ksp = [M3+]2[X2−]3

s mol/L of M2X3(s) dissolves to reach equilibrium
Change −s → +2s +3s
Equil. 2s 3s
3.60 × 10 −7 g 1 mol M 2 X 3
Ksp = (2s)2(3s)3 = 108s5 ; s = × = 1.25 × 10 −9 mol/L
L 288 g
Ksp = 108(1.25 × 10 −9 )5 = 3.30 × 10 −43
103. a. Because both solids dissolve to produce three ions in solution, we can compare values of
Ksp to determine relative solubility. Because the Ksp for CaF2 is the smallest, CaF2(s) has
the smallest molar solubility.
b. We must calculate molar solubilities because each salt yields a different number of ions
when it dissolves.
Ca3(PO4)2(s) ⇌ 3 Ca2+(aq) + 2 PO43−(aq) Ksp = 1.3 × 10−32

Equil. 3s 2s
Ksp = [Ca2+]3[PO43−]2 = (3s)3(2s)2 = 108s5, s = (1.3 × 10−32/108)1/5 = 1.6 × 10−7 mol/L
FePO4(s) ⇌ Fe3+(aq) + PO43−(aq) Ksp = 1.0 × 10−22

Equil. s s
Ksp = [Fe3+][PO43−] = s2, s = 1.0 × 10 −22 = 1.0 × 10−11 mol/L
FePO4 has the smallest molar solubility.
104. Ba(OH)2(s) ⇌ Ba2+(aq) + 2 OH−(aq) Ksp = [Ba2+][OH−]2 = 5.0 × 10 −3

Initial s = solubility (mol/L) 0 ~0 (Ignoring OH− from water.)
Equil. s 2s
Ksp = 5.0 × 10 −3 = s(2s)2 = 4s3, s = 0.11 mol/L
Assumption good, the amount of OH− from the autoionization of H2O can be ignored.
[OH−] = 2s = 2(0.11) = 0.22 mol/L; pOH = 0.66, pH = 13.34
Sr(OH)2(s) ⇌ Sr2+(aq) + 2 OH−(aq) Ksp = [Sr2+][OH−]2 = 3.2 × 10 −4

Equil. s 2s
Ksp = 3.2 × 10 −4 = 4s3, s = 0.043 mol/L; asssumption good.
[OH−] = 2(0.043) = 0.086 M; pOH = 1.07, pH = 12.93
Ca(OH)2(s) ⇌ Ca2+(aq) + 2 OH−(aq) Ksp = [Ca2+][OH−]2 = 1.3 × 10 −6

Equil. s 2s
Ksp = 1.3 × 10 −6 = 4s3, s = 6.9 × 10 −3 mol/L; assumption good.
[OH−] = 2(6.9 × 10 −3 ) = 1.4 × 10 −2 mol/L; pOH = 1.85, pH = 12.15
105. Let s = solubility of Co(OH)3 in mol/L.
Co(OH)3(s) ⇌ Co3+(aq) + 3 OH−(aq)

Initial 0 1.0 × 10 −7 M (from water)
s mol/L of Co(OH)3(s) dissolves to reach equilibrium = molar solubility
Equil. s 1.0 × 10 −7 + 3s
Ksp = 2.5 × 10 −43 = [Co3+][OH−]3 = (s)(1.0 × 10 −7 + 3s)3 ≈ s(1.0 × 10 −7 )3
2.5 × 10 −43
s= = 2.5 × 10 −22 mol/L; assumption good (1.0 × 10 −7 + 3s ≈ 1.0 × 10 −7 ).
1.0 × 10 − 21
106. a. Ag2SO4(s) ⇌ 2 Ag+(aq) + SO42−(aq)

Equil. 2s s
Ksp = 1.2 × 10−5 = [Ag+]2[SO42−] = (2s)2s = 4s3, s = 1.4 × 10−2 mol/L
b. Ag2SO4(s) ⇌ 2 Ag+(aq) + SO42−(aq)

Initial s = solubility (mol/L) 0.10 M 0
Equil. 0.10 + 2s s
Ksp = 1.2 × 10−5 = (0.10 + 2s)2(s) ≈ (0.10)2(s), s = 1.2 × 10−3 mol/L; assumption good.
c. Ag2SO4(s) ⇌ 2 Ag+(aq) + SO42−(aq)

Initial s = solubility (mol/L) 0 0.20 M
Equil 2s 0.20 + s
1.2 × 10−5 = (2s)2(0.20 + s) ≈ 4s2(0.20), s = 3.9 × 10−3 mol/L; assumption good.
Note: Comparing the solubilities in parts b and c to part a illustrates that the solubility of
a salt decreases when a common ion is present.
107. a. Fe(OH)3(s) ⇌ Fe3+(aq) + 3 OH−(aq)

Initial 0 1 × 10 −7 M (from water)
s mol/L of Fe(OH)3(s) dissolves to reach equilibrium = molar solubility
Equil. s 1 × 10 −7 + 3s
Ksp = 4 × 10 −38 = [Fe3+][OH−]3 = (s)(1 × 10 −7 + 3s)3 ≈ s(1 × 10−7)3
s = 4 × 10 −17 mol/L; assumption good (3s << 1 × 10−7)
b. Fe(OH)3(s) ⇌ Fe3+(aq) + 3 OH−(aq) pH = 5.0, [OH−] = 1 × 10 −9 M

Initial 0 1 × 10-9 M (buffered)
s mol/L dissolves to reach equilibrium
Change −s → +s (assume no pH change in
buffer)
−9
Equil. s 1 × 10
Ksp = 4 × 10 −38 = [Fe3+][OH−]3 = (s)(1 × 10 −9 )3, s = 4 × 10 −11 mol/L = molar solubility

c. Fe(OH)3(s) ⇌ Fe3+(aq) + 3 OH-(aq) pH = 11.0, [OH−] = 1 × 10 −3 M

Initial 0 0.001 M (buffered)
s mol/L dissolves to reach equilibrium
Change −s → +s (assume no pH change)
Equil. s 0.001
Ksp = 4 × 10 −38 = [Fe3+][OH−]3 = (s)(0.001)3, s = 4 × 10 −29 mol/L = molar solubility
Note: As [OH−] increases, solubility decreases. This is the common ion effect.
108. a. PbI2(s) ⇌ Pb2+(aq) + 2 I−(aq)

Equil. s 2s
Ksp = 1.4 × 10−8 = [Pb2+][I−]2 = 4s3, s = 1.5 × 10−3 mol/L
b. PbI2(s) ⇌ Pb2+(aq) + 2 I−(aq)

Equil. 0.10 + s 2s
1.4 × 10−8 = (0.10 + s)(2s)2 ≈ (0.10)(2s)2 = (0.40)s2, s = 1.9 × 10−4 mol/L
Assumption good.
c. PbI2(s) ⇌ Pb2+(aq) + 2 I−(aq)

Equil. s 0.010 + 2s
1.4 × 10−8 = (s)(0.010 + 2s)2 ≈ (s)(0.010)2, s = 1.4 × 10−4 mol/L; assumption good.
Note that in parts b and c, the presence of a common ion decreases the solubility as
compared to the solubility of PbI2(s) in water.
109. Ca3(PO4)2(s) ⇌ 3 Ca2+(aq) + 2 PO43-(aq)

Initial 0 0.20 M
s mol/L of Ca3(PO4)2(s) dissolves to reach equilibrium
Equil. 3s 0.20 + 2s
Ksp = 1.3 × 10 −32 = [Ca2+]3[PO43−]2 = (3s)3(0.20 + 2s)2
Assuming 0.20 + 2s ≈ 0.20: 1.3 × 10 −32 = (3s)3(0.20)2 = 27s3(0.040)
s = molar solubility = 2.3 × 10 −11 mol/L; assumption good.

110. Ce(IO3)3(s) ⇌ Ce3+(aq) + 3 IO3−(aq)

Equil. s 0.20 + 3s
Ksp = [Ce3+][IO3−]3 = s(0.20 + 3s)3
From the problem, s = 4.4 × 10−8 mol/L; solving for Ksp:
Ksp = (4.4 × 10−8) × [0.20 + 3(4.4 × 10−8)]3 = 3.5 × 10−10
111. ZnS(s) ⇌ Zn2+(aq) + S2−(aq) Ksp = [Zn2+][S2−]

Equil. 0.050 + s s
Ksp = 2.5 × 10 −22 = (0.050 + s)(s) ≈ (0.050)s, s = 5.0 × 10 −21 mol/L; assumption good.
5.0 × 10 −21 mol ZnS 97.45 g ZnS
Mass ZnS that dissolves = 0.3000 L × × = 1.5 × 10 −19 g
L mol
112. For 99% of the Mg2+ to be removed, we need, at equilibrium, [Mg2+] = 0.01(0.052 M). Using
the Ksp equilibrium constant, calculate the [OH−] required to reach this reduced [Mg2+].
Mg(OH)2(s) ⇌ Mg2+(aq) + 2 OH−(aq) Ksp = 8.9 × 10 −12
8.9 × 10 −12 = [Mg2+][OH−]2 = [0.01(0.052 M)] [OH−]2, [OH−] = 1.3 × 10 −4 M (extra sig. fig.)
pOH = −log(1.3 × 10 −4 ) = 3.89; pH = 10.11; at a pH = 10.1, 99% of the Mg2+ in seawater will
be removed as Mg(OH)2(s).
113. If the anion in the salt can act as a base in water, then the solubility of the salt will increase as
the solution becomes more acidic. Added H+ will react with the base, forming the conjugate
acid. As the basic anion is removed, more of the salt will dissolve to replenish the basic anion.
The salts with basic anions are Ag3PO4, CaCO3, CdCO3 and Sr3(PO4)2. Hg2Cl2 and PbI2 do not
have any pH dependence because Cl− and I− are terrible bases (the conjugate bases of a strong
acids).
+
excess H
Ag3PO4(s) + H+(aq) → 3 Ag+(aq) + HPO42−(aq) 3 Ag+(aq) + H3PO4(aq)
+
excess H
CaCO3(s) + H → Ca + HCO3
+ 2+ −
Ca2+ + H2CO3 [H2O(l) + CO2(g)]
+
excess H
CdCO3(s) + H → Cd + HCO3−
+ 2+
Cd2+ + H2CO3 [H2O(l) + CO2(g)]
+
excess H
Sr3(PO4)2(s) + 2 H+ → 3 Sr2+ + 2 HPO42− 3 Sr2+ + 2 H3PO4
114. The relevant equations are:
2 Ag+(aq) + CrO42−(aq) ⇌ Ag2CrO4(s); Ag+(aq) + Cl−(aq) ⇌ AgCl(s)

(red) (white)
In the first test tube, Ag+ and NO3− ions are present. As CrO42− is added, the red precipitate
Ag2CrO4 forms, leaving some Ag+ and CrO42− in equilibrium with the red precipitate (Na+
and NO3− spectator ions are also present). As Cl− is added, the white precipitate AgCl forms,
lowering the concentration of Ag+. As Ag+ is removed, the equilibrium of the first equation
above is shifted to the left to produce more Ag+, resulting in the dissolution of the red
precicipatate [Ag2CrO4(s)]. As more of the CrO42− ion goes into solution, the solution turns
yellow due to the presence of the yellow CrO42−(aq) ion. Because AgCl(s) forms in
preference to Ag2CrO4(s), AgCl is less soluble than Ag2CrO4. This can be verified by
calculating the molar solubilities from the Ksp values given in Table 8.5 of the text.
Ag2CrO4(s) ⇌ 2 Ag+(aq) + CrO42−(aq)

Initial 0 0
Change −s → +2s +s
Equil. 2s s
(2s)2(s) = Ksp = 9.0 × 10−12, s = molar solubility = 1.3 × 10−4 mol/L
AgCl(s) ⇌ Ag+(aq) + Cl−(aq)

Initial 0 0
Equil. s s
s2 = Ksp = 1.6 × 10−10, s = 1.3 × 10−5 mol/L; Ag2CrO4(s) is more soluble than AgCl(s).
115. a. AgF b. Pb(OH)2 c. Sr(NO2)2 d. Ni(CN)2
All these salts have anions that are bases. The anions of the other choices are conjugate bases
of strong acids. They have no basic properties in water and, therefore, do not have solubili-
ties that depend on pH.
0.020 mmol
75.0 mL ×
116. [Ba2+]0 = mL = 7.5 × 10−3 M
200. mL
0.040 mmol
125 mL ×
[SO42−]0 = mL = 2.5 × 10−2 M
200. mL
Q = [Ba2+]0[SO42−]0 = (7.5 × 10−3)(2.5 × 10−2) = 1.9 × 10−4 > Ksp (1.5 × 10−9)
A precipitate of BaSO4(s) will form.

BaSO4(s) ⇌ Ba2+(aq) + SO42−(aq)

Before 0.0075 M 0.025 M
Let 0.0075 mol/L Ba2+ react with SO42− to completion because Ksp << 1.
Change ← −0.0075 −0.0075 Reacts completely
After 0 0.0175 New initial (carry extra sig. fig.)
s mol/L BaSO4 dissolves to reach equilibrium
Equil. s 0.0175 + s
Ksp = 1.5 × 10−9 = [Ba2+][SO42−] = (s)(0.0175 + s) ≈ s(0.0175)
s = 8.6 × 10−8 mol/L; [Ba2+] = 8.6 × 10−8 M; [SO42−] = 0.018 M; assumption good.
0.150 L(1.0 × 10 −4 mol / L)

117. [BaBr2]0 = = 6.0 × 10−5 M
0.250 L
0.100 L(6.0 × 10 −4 mol / L)

[K2C2O4]0 = = 2.4 × 10−4 M
0.250 L
Q = [Ba2+]0[C2O42−]0 = (6.0 × 10−5)(2.4 × 10−4) = 1.5 × 10−8 M
Because Q < Ksp, BaC2O4(s) will not precipitate. The final concentration of ions will be:
[Ba2+] = 6.0 × 10−5 M, [Br−] = 1.2 × 10−4 M
[K+] = 4.8 × 10−4 M, [C2O42−] = 2.4 × 10−4 M
118. 50.0 mL × 0.10 M = 5.0 mmol Pb2+; 50.0 mL × 1.0 M = 50. mmol Cl−. For this solution, Q >
Ksp, so PbCl2 precipitates. Assume precipitation of PbCl2(s) is complete. 5.0 mmol Pb2+
requires 10. mmol of Cl− for complete precipitation, which leaves 40. mmol Cl− in excess. Now
let some of the PbCl2(s) re-dissolve to establish equilibrium
PbCl2(s) ⇌ Pb2+(aq) + 2 Cl−(aq)
Initial 0 40.0 mmol/100.0 mL

s mol/L of PbCl2(s) dissolves to reach equilibrium
Equil. s 0.40 + 2s
Ksp = [Pb2+][Cl−]2, 1.6 × 10−5 = s(0.40 + 2s)2 ≈ s(0.40)2
s = 1.0 × 10−4 mol/L; assumption good.
At equilibrium:
[Pb2+] = s = 1.0 × 10−4 mol/L and [Cl−] = 0.40 + 2s, 0.40 + 2(1.0 × 10−4) = 0.40 M
119. Al(OH)3(s) ⇌ Al3+(aq) + 3 OH−(aq) Ksp = 2 × 10−32
Q = 2 × 10 −32 = [Al3+ ]0[OH − ]30 = (0.2) [OH − ]30 , [OH−]0 = 4.6 × 10 −11 (carrying extra sig. fig.)
pOH = −log(4.6 × 10−11) = 10.3; when the pOH of the solution equals 10.3, Ksp = Q. For
precipitation, we want Q > Ksp. This will occur when [OH−]0 > 4.6 × 10−11 or when pOH
< 10.3. Because pH + pOH = 14.00, precipitation of Al(OH)3(s) will begin when pH > 3.7
because this corresponds to a solution with pOH < 10.3.
120. For each lead salt, we will calculate the [Pb2+]0 necessary for Q = Ksp. Any [Pb2+]0 greater
than this value will cause precipitation of the salt (Q > Ksp).
PbF2(s) ⇌ Pb2+(aq) + 2 F−(aq) Ksp = 4 × 10−8; Q = 4 × 10−8 = [Pb 2+ ]0 [F − ]02

4 × 10 −8
[Pb2+]0 = =4M
(1 × 10 − 4 ) 2
PbS(s) ⇌ Pb2+(aq) + S2−(aq) Ksp = 7 × 10−29; Q = 7 × 10−29 = [Pb2+]0[S2−]0

7 × 10 −29
[Pb2+]0 = = 7 × 10−25 M
1 × 10 − 4
Pb3(PO4)2(s) ⇌ 3 Pb2+(aq) + 2 PO43−(aq) Ksp = 1 × 10−54
Q = 1 × 10−54 = [Pb 2+ ]30[PO 4 3− ]02

1/ 3
 1 × 10 −54 
[Pb ]0 = 
2+
−4 2 
= 5 × 10−16 M
 (1 × 10 ) 
From the calculated [Pb2+]0, the least soluble salt is PbS(s), and it will form first. Pb3(PO4)2(s)
will form second, and PbF2(s) will form last because it requires the largest [Pb2+]0 in order for
precipitation to occur.
121. Ag3PO4(s) ⇌ 3 Ag+(aq) + PO43−(aq); when Q is greater than Ksp, precipitation will occur. We
will calculate the [Ag+]0 necessary for Q = Ksp. Any [Ag+]0 greater than this calculated number
will cause precipitation of Ag3PO4(s). In this problem, [PO43−]0 = [Na3PO4]o =
1.0 × 10−5 M.
Ksp = 1.8 × 10−18; Q = 1.8 × 10−18 = [Ag+]03[PO43−]0 = [Ag+]03(1.0 × 10−5 M)

1/ 3
 1.8 × 10 −18 
[Ag ]0 = 
+
−5 
 , [Ag+]0 = 5.6 × 10−5 M
 1.0 × 10 
When [Ag+]0 = [AgNO3]0 is greater than 5.6 × 10−5 M, Ag3PO4(s) will precipitate.
122. From Table 8.5, Ksp for NiCO3 = 1.4 × 10−7 and Ksp for CuCO3 = 2.5 × 10−10. From the Ksp
values, CuCO3 will precipitate first because it has the smaller Ksp value and will be least
soluble. For CuCO3(s), precipitation begins when:
K sp , CuCO 3 2.5 × 10 −10
[CO32−] = = = 1.0 × 10−9 M CO32−
[Cu 2+ ] 0.25 M
For NiCO3(s) to precipitate:
K sp , NiCO3 1.4 × 10 −7
[CO32−] = = = 5.6 × 10−7 M CO32−
[ Ni 2+ ] 0.25 M
Determining the [Cu2+] when NiCO3(s) begins to precipitate:
K sp , CuCO 3 2.5 × 10 −10
[Cu2+] = 2−
= = 4.5 × 10−4 M Cu2+
[CO 3 ] 5.6 × 10 −7 M
For successful separation, 1% Cu2+ or less of the initial amount of Cu2+ (0.25 M) must be
present before NiCO3(s) begins to precipitate. The percent of Cu2+ present when NiCO3(s)
begins to precipitate is:
4.5 × 10 −4 M
× 100 = 0.18% Cu2+
0.25 M
Because less than 1% Cu2+ remains of the initial amount, the metals can be separated through
slow addition of Na2CO3(aq).
123. + 2+ 2+
a. Ag , Mg , Cu
NaCl(aq)
2+ +
AgCl(s) Mg , Cu2
-
NH3(aq) - contains OH
2+
Mg(OH)2(s) Cu(NH3)4 (aq)
H2S(aq)
CuS(s)
b. 2+ 2+ 2+
Pb , C a , Fe
NaCl(aq)
2+ 2+
PbC l2 (s) Ca , F e
Na2SO 4 (aq) or H 2 SO 4(aq)
2+
CaSO 4(s) Fe
H2 S(aq) - make basic
FeS(s)
- - -
c. Cl , Br , I
AgNO3(aq)
AgCl(s), AgBr(s), AgI(s)
NH3(aq)
+ -
AgBr(s) + AgI(s) Ag(NH3)2 (aq) + Cl (aq)
Na2S2O3
- -
AgI(s) Ag(S2O3)23 (aq) + Br (aq)
d. Pb2+, Bi3+
Na2SO4(aq) or H2SO4(aq)
PbSO4(s) Bi3+
H2S(aq) - make basic

Bi2S3(s)
124. Unlike AgCl(s), PbCl2(s) shows a significant increase in solubility with an increase in
temperature. Hence add NaCl to the solution containing the metal ion to form the chloride
salt precipitate, and then heat the solution. If the precipitate dissolves, then PbCl2 is present,
and the metal ion is Pb2+. If the precipitate does not dissolve with an increase in temperature,
then AgCl is the precipitate, and Ag+ is the metal ion present.
125. S2− is a very basic anion and reacts significantly with H+ to form HS− (S2− + H+ ⇌ HS−). Thus,
the actual concentration of S2− in solution depends on the amount of H+ present. In basic
solutions, little H+ is present, which shifts the above equilibrium to the left. In basic solutions,
the S2− concentration is relatively high. So, in basic solutions, a wider range of sulfide salts
will precipitate. However, in acidic solutions, added H+ shifts the equilibrium to the right
resulting in a lower S2− concentration. In acidic solutions, only the least soluble sulfide salts
will precipitate out of solution.
Complex Ion Equilibria

126. Mn2+ + C2O42− ⇌ MnC2O4 K1 = 7.9 × 103
MnC2O4 + C2O42− ⇌ Mn(C2O4)22- K2 = 7.9 × 101
Mn2+(aq) + 2 C2O42−(aq) ⇌ Mn(C2O4)22−(aq) Kf = K1K2 = 6.2 × 105
127. Hg2+(aq) + 2 I−(aq) → HgI2(s), orange ppt; HgI2(s) + 2 I−(aq) → HgI42−(aq)

Soluble complex ion
128. Ag+(aq) + Cl−(aq) ⇌ AgCl(s), white ppt.; AgCl(s) + 2 NH3(aq) ⇌ Ag(NH3)2+(aq) + Cl−(aq)
Ag(NH3)2+(aq) + Br−(aq) ⇌ AgBr(s) + 2 NH3(aq), pale yellow ppt. = AgBr(s)
AgBr(s) + 2 S2O32−(aq) ⇌ Ag(S2O3)23−(aq) + Br−(aq)
Ag(S2O3)23−(aq) + I−(aq) ⇌ AgI(s) + 2 S2O32−(aq), yellow ppt. = AgI(s)
The least soluble salt (smallest Ksp value) must be AgI because it forms in the presence of
Cl−and Br−. The most soluble salt (largest Ksp value) must be AgCl because it forms initially
but never re-forms. The order of Ksp values is Ksp (AgCl) > Ksp (AgBr) > Ksp (AgI).
The order of formation constants is Kf [Ag(S2O3)23−] > Kf [Ag(NH3)2+] because addition of

S2O32− causes the AgBr(s) precipitate to dissolve, but the presence of NH3 was unable to prevent
AgBr(s) from forming. This assumes concentrations are about equal.
65 g KI 1 mol KI
129. × = 0.78 M KI
0.500 L 166.0 g KI
The formation constant for HgI42− is an extremely large number. Because of this, we will let
the Hg2+ and I− ions present initially react to completion and then solve an equilibrium
problem to determine the Hg2+ concentration.
Hg2+(aq) + 4 I−(aq) ⇌ HgI42−(aq) K = 1.0 × 1030

Before 0.010 M 0.78 M 0
Change −0.010 −0.040 → +0.010 Reacts completely (K large)
After 0 0.74 0.010 New initial
x mol/L HgI42− dissociates to reach equilibrium
Change +x +4x ← −x
Equil. x 0.74 + 4x 0.010 − x
2−
30 [HgI 4 ] (0.010 − x)
K = 1.0 × 10 = 2+ − 4
= ; making usual assumptions:
[Hg ][I ] ( x)(0.74 + 4 x) 4
(0.010)
1.0 × 1030 ≈ , x = [Hg2+] = 3.3 × 10−32 M ; assumptions good.
( x)(0.74) 4
Note: 3.3 × 10−32 mol/L corresponds to one Hg2+ ion per 5 × 107 L. It is very reasonable to
approach the equilibrium in two steps. The reaction does essentially go to completion.
130. Fe3+(aq) + 6 CN−(aq) ⇌ Fe(CN)63−(aq) K = 1 × 1042

Initial 0 2.0 M 0.090 mol/0.60 L = 0.15 M
x mol/L Fe(CN)63− dissociates to reach equilibrium
Equil. x 2.0 + 6x 0.15 − x
3−
[Fe(CN ) 6 ] (0.15 − x) 0.15
K = 1 × 1042 = 3+ − 6
= , 1 × 1042 ≈
[Fe ][CN ] ( x)(2.0 + 6 x) 6
x(2.0) 6
x = [Fe3+] = 2 × 10−45 M; [Fe(CN)63−] = 0.15 M − x = 0.15 M; assumptions good.
131. [Be2+]0 = 5.0 × 10 −5 M and [F−]0 = 4.0 M because equal volumes of each reagent are mixed,
so all concentrations given in the problem are diluted by a factor of one-half.
Because the K values are large, assume all reactions go to completion, and then solve an
equilibrium problem.
Be2+(aq) + 4 F−(aq) ⇌ BeF42−(aq) K = K1K2K3K4 = 7.5 × 1012

Before 5.0 × 10 −5 M 4.0 M 0
After 0 4.0 M 5.0 × 10 −5 M
Equil. x 4.0 + 4x 5.0 × 10 −5 − x
[BeF4 2− ] 5.0 × 10 −5 − x 5.0 × 10 −5

K = 7.5 × 1012 = = ≈
[Be 2+ ][F − ] 4 x (4.0 + 4 x) 4 x (4.0) 4
x = [Be2+] = 2.6 × 10 −20 M; assumptions good. [F−] = 4.0 M; [BeF42−] = 5.0 × 10−5 M
Now use the stepwise K values to determine the other concentrtations.
[BeF+ ] [BeF+ ]
K1 = 7.9 × 10 4 = 2+ −
= − 20
, [BeF+] = 8.2 × 10 −15 M
[Be ][F ] (2.6 × 10 )(4.0)
[BeF2 ] [BeF2 ]
K2 = 5.8 × 103 = + −
= −15
, [BeF2] = 1.9 × 10 −10 M
[BeF ][F ] (8.2 × 10 )(4.0)
[BeF3 − ] [BeF3 − ]
K3 = 6.1 × 10 2 = −
= −10
, [BeF3−] = 4.6 × 10 −7 M
[BeF2 ][F ] (1.9 × 10 )(4.0)
132. AgCl(s) ⇌ Ag+ + Cl− Ksp = 1.6 × 10 −10

+
Ag + 2 NH3 ⇌ Ag(NH3)2+ Kf = 1.7 × 107
AgCl(s) + 2 NH3(aq) ⇌ Ag(NH3)2+(aq) + Cl−(aq) K = Ksp × Kf = 2.7 × 10 −3
AgCl(s) + 2 NH3 ⇌ Ag(NH3)2+ + Cl−

Initial 1.0 M 0 0
s mol/L of AgCl(s) dissolves to reach equilibrium = molar solubility
Equil. 1.0 – 2s s s
+
[Ag( NH 3 ) 2 ][Cl − ] s2
K = 2.7 × 10 −3 = = ; taking the square root:
[ NH 3 ]2 (1.0 − 2 s ) 2
s
= (2.7 × 10 −3 )1/2 = 5.2 × 10 −2 , s = 4.7 × 10 −2 mol/L
1 .0 − 2 s
In pure water, the solubility of AgCl(s) is (1.6 × 10 −10 )1/2 = 1.3 × 10 −5 mol/L. Notice how the
presence of NH3 increases the solubility of AgCl(s) by over a factor of 3500.
133. a. Cu(OH)2 ⇌ Cu2+ + 2 OH− Ksp = 1.6 × 10−19

Cu2+ + 4 NH3 ⇌ Cu(NH3)42+ Kf = 1.0 × 1013
Cu(OH)2(s) + 4 NH3(aq) ⇌ Cu(NH3)42+(aq) + 2 OH−(aq) K = KspKf = 1.6 × 10−6
b. Cu(OH)2(s) + 4 NH3 ⇌ Cu(NH3)42+ + 2 OH− K = 1.6 × 10-6

Initial 5.0 M 0 0.0095 M
s mol/L Cu(OH)2 dissolves to reach equilibrium
Equil. 5.0 − 4s s 0.0095 + 2s
2+
[Cu ( NH 3 ) 4 ][OH − ]2 s (0.0095 + 2 s) 2
K = 1.6 × 10−6 = =
[ NH 3 ]4 (5.0 − 4 s) 4
s (0.0095) 2
If s is small: 1.6 × 10−6 = , s = 11. mol/L
(5.0 ) 4
Assumptions are not good. We will solve the problem by successive approximations.
1.6 × 10 −6 (5.0 − 4 sguess ) 4
scalc = ; the results from six trials are:
(0.0095 + 2 sguess ) 2
sguess: 0.10, 0.050, 0.060, 0.055, 0.056
scalc: 1.6 × 10−2, 0.071, 0.049, 0.058, 0.056
Thus the solubility of Cu(OH)2 is 0.056 mol/L in 5.0 M NH3.

134. a. CuCl(s) ⇌ Cu+(aq) + Cl−(aq)

Equil. s s
Ksp = 1.2 × 10−6 = [Cu+][Cl−] = s2, s = 1.1 × 10−3 mol/L
b. Cu+ forms the complex ion CuCl2- in the presence of Cl-. We will consider both the Ksp
reaction and the complex ion reaction at the same time.
CuCl(s) ⇌ Cu+(aq) + Cl−(aq) Ksp = 1.2 × 10−6

Cu+(aq) + 2 Cl−(aq) ⇌ CuCl2−(aq) Kf = 8.7 × 104
CuCl(s) + Cl−(aq) ⇌ CuCl2−(aq) K = Ksp × Kf = 0.10
CuCl(s) + Cl− ⇌ CuCl2−

Initial 0.10 M 0
Equil. 0.10 − s s where s = solubility of CuCl(s) in mol/L
−
[CuCl 2 ] s
K = 0.10 = −
= , 1.0 × 10−2 − (0.10)s = s
[Cl ] 0.10 − s
(1.10)s = 1.0 × 10−2, s = 9.1 × 10−3 mol/L
135. AgBr(s) ⇌ Ag+ + Br- Ksp = 5.0 × 10 −13

Ag + 2 S2O32− ⇌ Ag(S2O3)23−
+
Kf = 2.9 × 1013
AgBr(s) + 2 S2O32− ⇌ Ag(S2O3)23− + Br− K = Ksp × Kf = 14.5 (Carry extra sig. figs.)
AgBr(s) 2 S2O32−(aq) ⇌ Ag(S2O3)23−(aq) + Br−aq)

+
Initial 0.500 M 0 0
s mol/L AgBr(s) dissolves to reach equilibrium
Change −s −2s → +s +s
Equil. 0.500 − 2s s s
s2
K= = 14.5; taking the square root of both sides:
(0.500 − 2 s ) 2
s
= 3.81, s = 1.91 − (7.62)s, s = 0.222 mol/L
0.500 − 2 s
0.222 mol AgBr 187.8 g AgBr

1.00 L × × = 41.7 g AgBr = 42 g AgBr
L mol AgBr
136. a. AgI(s) ⇌ Ag+(aq) + I−(aq) Ksp = [Ag+][I−] = 1.5 × 10−16

Equil. s s
Ksp = 1.5 × 10−16 = s2, s = 1.2 × 10−8 mol/L
b. AgI(s) ⇌ Ag+ + I− Ksp = 1.5 × 10−16

+
Ag + 2 NH3 ⇌ Ag(NH3)2+ Kf = 1.7 × 107
AgI(s) + 2 NH3(aq) ⇌ Ag(NH3)2+(aq) + I−(aq) K = Ksp × Kf = 2.6 × 10−9
AgI(s) + 2 NH3 ⇌ Ag(NH3)2+ + I−

Initial 3.0 M 0 0
s mol/L of AgI(s) dissolves to reach equilibrium = molar solubility
Equil. 3.0 − 2s s s
+
[Ag( NH 3 ) 2 ][I − ] s2 s2
K= = , 2.6 × 10 −9
≈ , s = 1.5 × 10−4 mol/L
[ NH 3 ]2 (3.0 − 2 s) 2 (3.0) 2
Assumption good.
c. The presence of NH3 increases the solubility of AgI. Added NH3 removes Ag+ from
solution by forming the complex ion, Ag(NH3)2+. As Ag+ is removed, more AgI(s) will
dissolve to replenish the Ag+ concentration.
137. Test tube 1: Added Cl− reacts with Ag+ to form a silver chloride precipitate. The net ionic
equation is Ag+(aq) + Cl-(aq) → AgCl(s). Test tube 2: Added NH3 reacts with Ag+ ions to form
a soluble complex ion, Ag(NH3)2+. As this complex ion forms, Ag+ is removed from the
solution, which causes the AgCl(s) to dissolve. When enough NH3 is added, all the silver
chloride precipitate will dissolve. The equation is AgCl(s) + 2 NH3(aq) → Ag(NH3)2+(aq) +
Cl−(aq). Test tube 3: Added H+ reacts with the weak base, NH3, to form NH4+. As NH3 is
removed from the Ag(NH3)2+ complex ion, Ag+ ions are released to solution and can then react
with Cl− to re-form AgCl(s). The equations are Ag(NH3)2+(aq) + 2 H+(aq) → Ag+(aq) + 2
NH4+(aq), and Ag+(aq) + Cl−(aq) → AgCl(s).
Additional Exercises
1.0 mmol
138. 1.0 mL × = 1.0 mmol Cd2+ added to the ammonia solution
mL
Thus [Cd2+]0 = 1.0 × 10−3 mol/L. We will first calculate the equilibrium Cd2+ concentration
using the complex ion equilibrium, and then determine if this Cd2+ concentration is large
enough to cause precipitation of Cd(OH)2(s).
Cd2+ + 4 NH3 ⇌ Cd(NH3)42+ Kf = 1.0 × 107
Before 1.0 × 10−3 M 5.0 M 0
Change −1.0 × 10−3 −4.0 × 10−3 → +1.0 × 10−3 Reacts completely
After 0 4.996 ≈ 5.0 1.0 × 10 −3
New initial
x mol/L Cd(NH3)42+ dissociates to reach equilibrium
Equil. x 5.0 + 4x 0.0010 − x
(0.010 − x) (0.010)
Kf = 1.0 × 107 = ≈
( x)(5.0 + 4 x) 4
( x)(5.0) 4
x = [Cd2+] = 1.6 × 10−13 M; assumptions good. This is the maximum [Cd2+] possible. Now
we will determine if Cd(OH)2(s) forms at this concentration of Cd2+. In 5.0 M NH3 we can
calculate the pH:
NH3 + H2O ⇌ NH4+ + OH− Kb = 1.8 × 10−5

Initial 5.0 M 0 ~0
Equil. 5.0 − y y y
+
[ NH 4 ][OH − ] y2 y2
Kb = 1.8 × 10−5 = = ≈ , y = [OH−] = 9.5 × 10−3 M;
[ NH 3 ] 5.0 − y 5.0
Assumptions good. We now calculate the value of the solubility quotient, Q:
Q = [Cd2+][OH−]2 = (1.6 × 10−13)(9.5 × 10−3)2
Q = 1.4 × 10−17 < Ksp (5.9 × 10−15); therefore, no precipitate forms.
139. a. The optimum pH for a buffer is when pH = pKa. At this pH a buffer will have equal
neutralization capacity for both added acid and base. As shown next, because the pKa for
TRISH+ is 8.1, the optimal buffer pH is about 8.1.
Kb = 1.19 × 10−6; Ka = Kw/Kb = 8.40 × 10−9; pKa = −log(8.40 × 10−9) = 8.076

[TRIS] [TRIS]
b. pH = pKa + log +
, 7.00 = 8.076 + log
[TRISH ] [TRISH + ]
[TRIS]
+
= 10-1.08 = 0.083 (at pH = 7.00)
[TRISH ]
[TRIS] [TRIS]
9.00 = 8.076 + log , = 100.92 = 8.3 (at pH = 9.00)
[TRISH ] [TRISH + ]
+
50.0 g TRIS 1 mol

c. × = 0.206 M = 0.21 M = [TRIS]
2.0 L 121.14 g
65.0 g TRISHCl 1 mol
× = 0.206 M = 0.21 M = [TRISHCl] = [TRISH+]
2.0 L 157.60 g
[TRIS] (0.21)
pH = pKa + log +
= 8.076 + log = 8.08
[TRISH ] (0.21)
The amount of H+ added from HCl is: (0.50 × 10−3 L) × 12 mol/L = 6.0 × 10−3 mol H+
The H+ from HCl will convert TRIS into TRISH+. The reaction is:
TRIS + H+ → TRISH+
−3
6.0 × 10
Before 0.21 M = 0.030 M 0.21 M
0.2005
After 0.18 0 0.24
Now use the Henderson-Hasselbalch equation to solve this buffer problem.

 0.18 
pH = 8.076 + log   = 7.95
 0.24 
140. Let’s abbreviate the carboxylic acid group in alanine as RCOOH and the amino group in
alanine as RNH2. The Ka reaction for the carboxylic acid group is:
RCOOH ⇌ RCOO− + H+ Ka = 4.5 × 10−7

From Le Chatelier’s principle, if we have a very acidic solution, a lot of H+ is present. This
drives the Ka reaction to the left, and the dominant form of the carboxylic acid group will be
RCOOH (an overall neutral charge). If we have a very basic solution, the excess OH− will
remove H+ from solution. As H+ is removed, the Ka reaction shifts right, and the dominant
form of the carboxylic acid group will be RCOO− (an overall 1− charged ion).
The Kb reaction for the amino group is:
RNH2 + H2O ⇌ RNH3+ + OH−
If we have a very acidic solution, the excess protons present will remove OH− from solution,
and the dominant form of the amino group will be RNH3+ (an overall 1+ charged ion). If we
have a very basic solution, a lot of OH− is present, and the dominant form of the amino group
will be RNH2 (an overall neutral charge).
In alanine, both an RCOOH group and an RNH2 group are present. The dominant form of
alanine in a very acidic solution will be the form with the protons attached to the two groups
that have acid-base properties. This form of alanine is:
which has an overall charge of 1+. The dominant form of alanine in a very basic solution will
be in the form with the protons removed from the two groups that have acid-base properties.
This form of alanine is:
CH3 O
−
H2N C C O
which has an overall charge of 1−.
141. In NH3, Cu2+ forms the soluble complex ion Cu(NH3)42+. This increases the solubility of
Cu(OH)2(s) because added NH3 removes Cu2+ from the equilibrium causing more Cu(OH)2(s)
to dissolve. In HNO3, H+ removes OH− from the Ksp equilibrium causing more Cu(OH)2(s) to
dissolve. Any salt with basic anions will be more soluble in an acid solution. AgC2H3O2(s)
will be more soluble in either NH3 or HNO3. This is because Ag+ forms the complex ion
Ag(NH3)2+, and C2H3O2− is a weak base, so it will react with added H+. AgCl(s) will be more
soluble only in NH3 due to Ag(NH3)2+ formation. In acid, Cl- is a horrible base, so it doesn’t
react with added H+. AgCl(s) will not be more soluble in HNO3.
142. i. This is the result when you have a salt that breaks up into two ions. Examples of these
salts (but not all) include AgCl, SrSO4, BaCrO4, and ZnCO3.
ii. This is the result when you have a salt that breaks up into three ions, either two cations
and one anion or one cation and two anions. Some examples are SrF2, Hg2I2, and
Ag2SO4.
iii. This is the result when you have a salt that breaks up into four ions, either three cations
and one anion (Ag3PO4) or one cation and three anions (ignoring the hydroxides, there
are no examples of this type of salt in Table 8.5).
iv. This is the result when you have a salt that breaks up into five ions, either three cations
and two anions [Sr3(PO4)2] or two cations and three anions (no examples of this type of
salt are in Table 8.5).
143. A best buffer is when pH ≈ pKa; these solutions have about equal concentrations of weak acid
and conjugate base. Therefore, choose combinations that yield a buffer where pH ≈ pKa; that
is, look for acids whose pKa is closest to the pH.
a. Potassium fluoride + HCl will yield a buffer consisting of HF (pKa = 3.14) and F−.
b. Benzoic acid + NaOH will yield a buffer consisting of benzoic acid (pKa = 4.19) and
benzoate anion.
c. Sodium acetate + acetic acid (pKa = 4.74) is the best choice for pH = 5.0 buffer since acetic
acid has a pKa value closest to 5.0.
d. HOCl and NaOH: This is the best choice to produce a conjugate acid-base pair with pH =
7.0. This mixture would yield a buffer consisting of HOCl (pKa = 7.46) and OCl−. Actually,
the best choice for a pH = 7.0 buffer is an equimolar mixture of ammonium chloride and
sodium acetate. NH4+ is a weak acid (Ka = 5.6 × 10−10), and C2H3O2− is a weak base (Kb =
5.6 × 10−10). A mixture of the two will give a buffer at pH = 7.0 because the weak acid and
weak base are the same strengths (Ka for NH4+ = Kb for C2H3O2−). NH4C2H3O2 is
commercially available, and its solutions are used for pH = 7.0 buffers.
e. Ammonium chloride + NaOH will yield a buffer consisting of NH4+ (pKa = 9.26) and
NH3.
144. For a titration of a strong acid with a strong base, the added OH- reacts completely with the
H+ present. To determine the pH, we calculate the concentration of excess H+ or OH− after the
neutralization reaction, and then calculate the pH.
0 mL: [H+] = 0.100 M from HNO3; pH = 1.000

0.100 mmol H +
4.0 mL: Initial mmol H+ present = 25.0 mL × = 2.50 mmol H+
mL
0.100 mmol OH −
mmol OH− added = 4.0 mL × = 0.40 mmol OH-
mL
0.40 mmol OH− reacts completely with 0.40 mmol H+: OH− + H+ → H2O
(2.50 − 0.40) mmol
[H+]excess = = 7.24 × 10 −2 M; pH = 1.140
(25.0 + 4.0) mL
We follow the same procedure for the remaining calculations.
(2.50 − 0.80) mmol
8.0 mL: [H+]excess = = 5.15 × 10 −2 M; pH = 1.288
33.0 mL
(2.50 − 1.25) mmol

12.5 mL: [H+]excess = = 3.33 × 10 −2 M; pH = 1.478
37.5 mL
(2.50 − 2.00) mmol

20.0 mL: [H+]excess = = 1.1 × 10 −2 M; pH = 1.96
45.0 mL
(2.50 − 2.40) mmol

24.0 mL: [H+]excess = = 2.0 × 10 −3 M; pH = 2.70
49.0 mL
(2.50 − 2.45) mmol

24.5 mL: [H+]excess = = 1 × 10 −3 M; pH = 3.0
49.5 mL
(2.50 − 2.49) mmol

24.9 mL: [H+]excess = = 2 × 10 −4 M; pH = 3.7
49.9 mL
25.0 mL: Equivalence point; we have a neutral solution because there is no excess H+ or
OH− remaining after the neutralization reaction. pH = 7.00
(2.51 − 2.50) mmol
25.1 mL: Base in excess; [OH−]excess = = 2 × 10 −4 M; pOH = 3.7
50.1 mL
pH = 14.00 – 3.7 = 10.3
(2.60 − 2.50) mmol

26.0 mL: [OH−]excess = = 2.0 × 10 −3 M; pOH = 2.70; pH = 11.30
51.0 mL
(2.80 − 2.50) mmol

53.0 mL
(3.00 − 2.50) mmol

55.0 mL
0.500 mmol
145. NaOH added = 50.0 mL × = 25.0 mmol NaOH
mL
0.289 mmol 1 mmol NaOH
NaOH left unreacted = 31.92 mL HCl × × = 9.22 mmol NaOH
mL mmol HCl
NaOH reacted with aspirin = 25.0 − 9.22 = 15.8 mmol NaOH

1 mmol aspirin 180.2 mg
15.8 mmol NaOH × × = 1420 mg = 1.42 g aspirin
2 mmol NaOH mmol
1.42 g
Purity = × 100 = 99.5%
1.427 g
Here, a strong base is titrated by a strong acid. The equivalence point will be at pH =
7.0. Bromthymol blue would be the best indicator since it changes color at pH ≈ 7 (from base
color to acid color). See Fig. 8.8 of the text.
ΔpH 2.43 − 3.14

146. At 4.0 mL NaOH added: = = 0.18
ΔmL 0 − 4.0
The other points are calculated in a similar fashion. The results are summarized and plotted
below. As can be seen from the plot, the advantage of this approach is that it is much easier
to accurately determine the location of the equivalence point.
mL pH |∆pH/∆mL|
0 2.43 −
4.0 3.14 0.18
8.0 3.53 0.098
12.5 3.86 0.073
20.0 4.46 0.080
24.0 5.24 0.20
24.5 5.6 0.7
24.9 6.3 2
25.0 8.28 20
25.1 10.3 20
26.0 11.30 1
28.0 11.75 0.23
30.0 11.96 0.11
147. At the equivalence point, P2− is the major species. P2− is a weak base in water because it is
the conjugate base of a weak acid.
P2− + H2O ⇌ HP− + OH−

0.5 g 1 mol
Initial × = 0.024 M 0 ~0 (carry extra sig. fig.)
0.1 L 204.2 g
[HP − ][OH − ] Kw 1.0 × 10 −14 −9 x2 x2
Kb = = = , 3.2 × 10 = ≈
P 2− Ka 10 −5.51 0.024 − x 0.024
Phenolphthalein would be the best indicator for this titration because it changes color at
pH ≈ 9 (from acid color to base color).
148. a. 1.00 L × 0.100 mol/L = 0.100 mol HCl added to reach stoichiometric point.
10.00 g
The 10.00-g sample must have contained 0.100 mol of NaA. = 100. g/mol
0.100 mol
b. 500.0 mL of HCl added represents the halfway point to equivalence. Thus pH = pKa =
5.00 and Ka = 1.0 × 10−5. At the equivalence point, enough H+ has been added to convert
all the A− present initially into HA. The concentration of HA at the equivalence point is:
0.100 mol
[HA]0 = = 0.0909 M
1.10 L
HA ⇌ H+ + A− Ka = 1.0 × 10−5
Equil. 0.0909 - x x x
x2 x2
Ka = 1.0 × 10−5 = ≈
0.0909 − x 0.0909
x = 9.5 × 10−4 M = [H+]; pH = 3.02; assumptions good.
149. CaF2(s) ⇌ Ca2+(aq) + 2 F−(aq) Ksp = [Ca2+][F−]2
We need to determine the F− concentration present in a 1.0 M HF solution. Solving the weak
acid equilibrium problem:
[H + ][F − ]
HF(aq) ⇌ H+(aq) + F−(aq) Ka =
[HF]
Initial 1.0 M ~0 0
x(x) x2
Ka = 7.2 × 10−4 = ≈ , x = [F−] = 2.7 × 10 −2 M; assumption good.
1.0 − x 1.0
Next, calculate the Ca2+ concentration necessary for Q = K sp, CaF2 .
Q = [Ca 2+ ]0 [F − ]02 , 4.0 × 10 −11 = [Ca 2+ ]0 (2.7 × 10 −2 ) 2 , [Ca 2+ ]0 = 5.5 × 10 −8 mol/L
5.5 × 10 −8 mol Ca 2+ 1 mol Ca ( NO3 ) 2 164.10 g Ca ( NO 3 ) 2

Mass Ca(NO3)2 = 1.0 L × × ×
L mol Ca 2+ mol
−6
= 9.0 × 10 g Ca ( NO 3 ) 2
For precipitation of CaF2(s) to occur, we need Q > Ksp. When 9.0 × 10 −6 g Ca ( NO 3 ) 2 has
been added to 1.0 L of solution, Q = Ksp. So precipitation of CaF2(s) will begin to occur
when just more than 9.0 × 10 −6 g Ca ( NO 3 ) 2 has been added.
150. Cr3+ + H2EDTA2− ⇌ CrEDTA− + 2 H+

Before 0.0010 M 0.050 M 0 1.0 × 10−6 M (Buffer)
Change −0.0010 −0.0010 → +0.0010 No change Reacts completely
After 0 0.049 0.0010 1.0 × 10−6 New initial
−
x mol/L CrEDTA dissociates to reach equilibrium
Change +x +x ← −x −
Equil. x 0.049 + x 0.0010 − x 1.0 × 10−6 (Buffer)
[CrEDTA − ][H + ] 2 (0.0010 − x) (1.0 × 10 −6 ) 2
Kf = 1.0 × 1023 = =
[Cr 3+ ][H 2 EDTA 2− ] (x)(0.049 + x)
(0.0010) (1.0 × 10 −12 )

1.0 × 1023 ≈ , x = [Cr3+] = 2.0 × 10−37 M; assumptions good.
x(0.049)
151. a. Pb(OH)2(s) ⇌ Pb2+ + 2 OH−

Initial s = solubility (mol/L) 0 1.0 × 10−7 M (from water)
Equil. s 1.0 × 10−7 + 2s
Ksp = 1.2 × 10−15 = [Pb2+][OH−]2 = s(1.0 × 10−7 + 2s)2 ≈ s(2s2) = 4s3
s = [Pb2+] = 6.7 × 10−6 M; assumption is good by the 5% rule.
b. Pb(OH)2(s) ⇌ Pb2+ + 2 OH−

Initial 0 0.10 M pH = 13.00, [OH−] = 0.10 M
s mol/L Pb(OH)2(s) dissolves to reach equilibrium
Equil. s 0.10 (Buffered solution)
1.2 × 10−15 = (s)(0.10)2, s = [Pb2+] = 1.2 × 10−13 M
c. We need to calculate the Pb2+ concentration in equilibrium with EDTA4-. Since K is large
for the formation of PbEDTA2−, let the reaction go to completion, and then solve an
equilibrium problem to get the Pb2+ concentration.
Pb2+ + EDTA4− ⇌ PbEDTA2− K = 1.1 × 1018

Before 0.010 M 0.050 M 0
0.010 mol/L Pb2+ reacts completely (large K)
After 0 0.040 0.010 New initial
x mol/L PbEDTA2− dissociates to reach equilibrium
Equil. x 0.040 + x 0.010 − x
(0.010 − x) 0.010
1.1 × 1018 = ≈ , x = [Pb2+] = 2.3 × 10−19 M; assumptions good.
( x)(0.040 + x) x(0.040)
Now calculate the solubility quotient for Pb(OH)2 to see if precipitation occurs. The
concentration of OH− is 0.10 M since we have a solution buffered at pH = 13.00.
Q = [Pb2+]0[OH−]02 = (2.3 × 10−19)(0.10)2 = 2.3 × 10−21 < Ksp (1.2 × 10−15)
Pb(OH)2(s) will not form since Q is less than Ksp.
152. Mg(OH)2(s) ⇌ Mg2+(aq) + 2 OH−(aq) Ksp = [Mg2+][OH−]2 = 8.9 × 10 −12

Initial s = solubility (mol/L) 0 ~0 (Ignoring OH− from water.)
Equil. s 2s
Ksp = 8.9 × 10 −12 = s(2s)2 = 4s3, s = 1.3 × 10 −4 mol/L
Assumption good, the amount of OH− from the autoionization of H2O can be ignored.
[OH−] = 2s = 2(1.3 × 10 −4 ) = 2.6 × 10 −4 mol/L; pOH = 3.59, pH = 10.41

Cd(OH)2(s) ⇌ Cd2+(aq) + 2 OH−(aq) Ksp = [Cd2+][OH−]2 = 5.9 × 10 −15

Equil. s 2s
Ksp = 5.9 × 10 −15 = 4s3, s = 1.1 × 10 −5 mol/L; asssumption good.
[OH−] = 2(1.1 × 10 −5 ) = 2.2 × 10 −5 M; pOH = 4.66, pH = 9.34
Pb(OH)2(s) ⇌ Pb2+(aq) + 2 OH−(aq) Ksp = [Pb2+][OH−]2 = 1.2 × 10 −15

Equil. s 2s
Ksp = 1.2 × 10 −15 = 4s3, s = 6.7 × 10 −6 mol/L; assumption good.
[OH−] = 2(6.7 × 10 −6 ) = 1.3 × 10 −5 mol/L; pOH = 4.89, pH = 9.11
153. HC2H3O2 ⇌ H+ + C2H3O2−; let C0 = initial concentration of HC2H3O2

−
[H + ][C 2 H 3O 2 ] [ H + ]2
From normal weak acid setup: Ka = 1.8 × 10−5 = =
[HC 2 H 3O 2 ] C 0 − [H + ]
(2.1 × 10 −3 ) 2
[H+] = 10−2.68 = 2.1 × 10−3 M; 1.8 × 10−5 = , C0 = 0.25 M
C 0 − (2.1 × 10 −3 )
25.0 mL × 0.25 mmol/mL = 6.3 mmol HC2H3O2
Need 6.3 mmol KOH = VKOH × 0.0975 mmol/mL, VKOH = 65 mL
154. In the final solution: [H+] = 10−2.15 = 7.1 × 10−3 M
Beginning mmol HCl = 500.0 mL × 0.200 mmol/mL = 100. mmol HCl
Amount of HCl that reacts with NaOH = 1.50 × 10−2 mmol/mL × V

7.1 × 10 −3 mmol final mmol H + 100. − 0.0150 V
= =
mL total volume 500.0 + V
3.6 + (7.1 × 10−3)V = 100. − (1.50 × 10−2)V, (2.21 × 10−2)V = 100. − 3.6
V = 4.36 × 103 mL = 4.36 L = 4.4 L NaOH
155. 0.400 mol/L × VNH 3 = mol NH3 = mol NH4+ after reaction with HCl at the equivalence point.
mol NH 4
+
0.400 × VNH 3
At the equivalence point: [NH4+]0 = = = 0.267 M
total volume 1.50 × VNH 3
NH4+ ⇌ H+ + NH3
Initial 0.267 M 0 0
Kw 1.0 × 10 −14 x2 x2
Ka = = , 5.6 × 10−10
= ≈
Kb 1.8 × 10 −5 0.267 − x 0.267
156. 50.0 mL × 0.100 M = 5.00 mmol NaOH initially
At pH = 10.50, pOH = 3.50, [OH−] = 10−3.50 = 3.2 × 10−4 M
mmol OH− remaining = 3.2 × 10−4 mmol/mL × 73.75 mL = 2.4 × 10−2 mmol
mmol OH− that reacted = 5.00 - 0.024 = 4.98 mmol
Because the weak acid is monoprotic, 23.75 mL of the weak acid solution contains 4.98
mmol HA.
4.98 mmol
[HA]0 = = 0.210 M
23.75 mL
157. HA + OH− → A− + H2O, where HA = acetylsalicylic acid

0.5106 mmol OH − 1 mmol HA
mmol HA present = 27.36 mL OH− × × = 13.97 mmol HA
mL OH − mmol OH −
2.51 g HA
Molar mass of HA = = 180. g/mol
13.97 × 10 −3 mol HA
To determine the Ka value, use the pH data. After complete neutralization of acetylsalicylic
acid by OH−, we have 13.97 mmol of A- produced from the neutralization reaction. A− will
react completely with the added H+ and re-form acetylsalicylic acid HA.
0.4524 mmol H +
mL
A− + H+ → HA
We have back titrated this solution to the halfway point to equivalence, where pH = pKa
(assuming HA is a weak acid). This is true because after H+ reacts completely, equal milliliters
of HA and A− are present, which only occurs at the halfway point to equivalence. Assuming
acetylsalicylic acid is a weak acid, then pH = pKa = 3.48. Ka = 10−3.48 = 3.3 × 10−4.
158. [X−]0 = 5.00 M and [Cu+]0 = 1.0 × 10−3 M since equal volumes of each reagent are mixed.
Because the K values are large, assume that the reaction goes completely to CuX32−; then
solve an equilibrium problem.
Cu+ + 3 X− ⇌ CuX32− K = K1K2K3 = 1.0 × 109

−3
Before 1.0 × 10 M 5.00 M 0
After 0 5.00 − 3(10−3) = 5.00 1.0 × 10−3
Equil. x 5.00 + 3x 1.0 × 10−3 − x
(1.0 × 10 −3 − x) 1.0 × 10 −3
K= , 1.0 × 10 9
≈ , x = [Cu+] = 8.0 × 10−15 M;
x(5.00 + 3 x) 3 x(5.00) 3
Assumptions good.
[CuX32−] = 1.0 × 10−3 − 8.0 × 10−15 = 1.0 × 10−3 M

2−
[CuX 3 ] (1.0 × 10 −3 )
K3 = −
3
, 1.0 × 10 = −
, [CuX2−] = 2.0 × 10−7 M
[CuX 2 ][X − ] [CuX 2 ](5.00)
Summarizing:
[CuX32−] = 1.0 × 10−3 M (answer a)

[CuX2−] = 2.0 × 10−7 M (answer b)
[Cu2+] = 8.0 × 10−15 M (answer c)
159. K a 3 is so small (4.8 × 10−13) that a break is not seen at the third stoichiometric point.
160. We will see only the first stoichiometric point in the titration of salicylic acid because K a 2 is
so small. For adipic acid, the Ka values are fairly close to each other. Both protons will be
titrated almost simultaneously, giving us only one break. The stoichiometric points will occur
when 1 mol of OH− is added per mole of salicylic acid present and when 2 mol of OH− is added
per mole of adipic acid present. Thus the 25.00-mL volume corresponded to the titration of
salicylic acid, and the 50.00-mL volume corresponded to the titration of adipic acid.
ChemWork Problems
161. a. Major species: HOC6H5, OC6H5− and Na+. Na+ has no acidic or basic properties. We
have a weak acid and its conjugate base present. This is a buffer solution.
HOC6H5 ⇌ OC6H5− + H+
Initial 0.85 M 0.80 M ~0
x mol/L HOC6H5 dissociates to reach equilibrium
Change –x → +x +x
Equil. 0.85 – x 0.80 + x x
−
[OC 6 H 5 ][H + ] (0.80 + x)( x) (0.80)( x)
Ka = 1.6 × 10 −10 = = ≈ (assuming x << 0.80)
[HOC 6 H 5 ] 0.85 − x 0.85
x = 1.7 × 10 −10 M = [H+]; assumptions good.

pH = –log(1.7 × 10 −10 ) = 9.77

Note: We would get the same answer using the Henderson-Hasselbalch equation. Use
whichever method you prefer.
b. Major species after HCl added: HOC6H5, OC6H5−, Na+, H+, Cl−; the added H+ from the
strong acid will react completely with the best base present (OC6H5−).
H+ + OC6H5− → HOC6H5
0.10 mol
Before 0.80 M 0.85 M
1.00 L
Change –0.10 M –0.10 M → +0.10 M Reacts completely
After 0 0.70 0.95
After all the H+ has reacted, we have a buffer solution (a solution containing a weak acid
and its conjugate base). Solving the buffer problem:
Initial 0.95 M 0.70 M ~0
Equil. 0.95 – x 0.70 + x x
−
[OC 6 H 5 ][H + ] (0.70 + x)( x) (0.70)( x)
Ka = 1.6 × 10 −10 = = ≈ (assuming x << 0.70)
[HOC 6 H 5 ] 0.95 − x 0.95
x = 2.2 × 10 −10 M = [H+]; assumptions good.
pH = –log(2.2 × 10 −10 ) = 9.66
c. Major species after NaOH added: HOC6H5, OC6H5−, Na+, and OH−. The added OH− from
the strong base will react completely with the best acid present (HOC6H5).
OH− + HOC6H5 → OC6H5− + H2O

Before 0.20 mol/1.00 L 0.85 M 0.80 M
Change –0.20 M –0.20 M → +0.20 M Reacts completely
After 0 0.65 1.00
After all the OH− reacts, we are left with a solution containing a weak acid (HOC6H5) and
its conjugate base (OC6H5−). This is a buffer problem.
Initial 0.65 M 1.00 M ~0
Equil. 0.65 – x 1.00 + x x
−
[OC 6 H 5 ][H + ] (1.00 + x)( x) (1.00)( x)
Ka = 1.6 × 10 −10 = = ≈ (assuming x << 0.65)
[HOC 6 H 5 ] 0.65 − x 0.65
x = 1.0 × 10 −10 M = [H+]; assumptions good. pH = –log(1.0 × 10 −10 ) = 10.00
162. We will use the Henderson-Hasselbalch equation to solve this problem.
pKa for NH4+ = –log(5.6 × 10–10) = 9.25

[NH 3 ] 0.52 M
pH = pKa + log +
, 9.00 = 9.25 + log +
[NH 4 ] [NH 4 ]
0.52 M
−0.25 = log +
, [NH4+] = [NH4Cl] = 0.92 M
[ NH 4 ]
163. A best buffer has large and equal quantities of weak acid and conjugate base. Because [acid]
[base]
= [base] for a best buffer, pH = pKa + log = pKa + 0 = pKa (pH ≈ pKa for a best
[acid]
buffer).
The best acid choice for a pH = 9.00 buffer would be the weak acid with a pKa closest to 9.0
or Ka ≈ 1 × 10−9. HOBr is the best choice in the Table (Ka = 2.0 × 10−9; pKa = 8.70). So the
best buffer choice for a pH = 9.00 buffer would be to use HOBr (b) and its conjugate base
OBr− (h).
164. a. False; the buffer with the largest concentrations has the highest buffer capacity.
b. True; when the base component of the buffer has a larger concentration than the acid
component, then pH > pKa.
c. True; as more of the acid component of the buffer is added, the pH will become more
acidic (pH will decrease).
d. False; for this buffer, pKa = −log(2.3 × 10−11) = 10.64. Here, we have more of the acid
component of the buffer than the base component. When this occurs, pH < pKa. So we
can say that for this situation, pH < 10.64, not that pH < 3.36.
e. True; when [weak acid] = [conjugate base] in a buffer, pH = pKa.
165. a. This is a strong acid (HI) titrated by a strong base (NaOH). Added OH− from the
strong base will react completely with the H+ present from the strong acid to produce
H2O.
0.250 mmol OH −
mL
0.100 mmol H +
mmol H+ present = 150.0 mL × = 15.0 mmol H+
mL
Note: The units millimoles are usually easier numbers to work with. The units for
molarity are moles per liter but are also equal to millimoles per milliliter.
H+ + OH− → H2O
After 10.0 mmol 0
10.0 mmol H +
The excess H+ determines the pH. [H+]excess = = 0.0588 M
150.0 mL + 20.0 mL
pH = −log(0.0588) = 1.231
b. For a strong acid-strong base titration, pH = 7.00 at the equivalence point. Because we
have 15.0 mmol of H+, we need 15.0 mmol of OH− to reach the equivalence point.
1 mL OH −
15.0 mmol OH− × = 60.0 mL OH−
0.250 mmol OH −
To reach the equivalence point where pH = 7.00, 60.0 mL of NaOH must be added.
166. This is a weak acid (HCN) titrated by a strong base (KOH).
a. Only weak acid is present. Solving the weak acid problem:
HCN ⇌ H+ + CN−
x mol/L HCN dissociates to reach equilibrium
x2 x2
Ka = 6.2 × 10−10 = ≈ , x = [H+] = 7.9 × 10−6 M
0.100 − x 0.100
b. The added OH− will react completely with the best acid present, HCN.
0.100 mmol HCN
mmol HCN present = 100.0 mL × = 10.0 mmol HCN
mL
0.100 mmol OH −
mL
HCN + OH− → CN− + H2O

Change −5.00 mmol −5.00 mmol → +5.00 mmol Reacts Completely
After reaction of all of the strong base, we have a buffer solution containing a weak acid
(HCN) and its conjugate base (CN−). We will use the Henderson-Hasselbalch equation to
solve for the pH where VT = total volume:
[CN − ]  5.00 mmol/VT 

pH = pKa + log = −log (6.2 × 10−10) + log  
[HCN]  5.0 mmol/VT 
 5.00 
pH = 9.21 + log   = 9.21 + 0.0 = 9.21
 5.0 
This is the halfway point to equivalence. In a weak acid-strong base titration, pH = pKa at
the halfway point to equivalence because [weak acid] = [conjugate base] at this point.
Also note that the total volume cancels in the Henderson-Hasselbalch equation. For the
[base]/[acid] term, the mole ratio equals the concentration ratio because the components of
the buffer are always in the same volume of solution.
c. mmol OH− added = 75.0 mL × 0.100 M = 7.50 mmol OH−; the same amount (10.0 mmol)
of HCN is present as before (it doesn’t change). Let the OH− react to completion, then see
what is remaining in solution after this reaction.

We have a buffer solution after all the OH− reacts to completion. Using the Henderson-
[CN − ]  7.50 mmol 
pH = 9.21 + log = 9.21 + log  
[HCN]  2.5 mmol 
pH = 9.21 + 0.48 = 9.69
d. The equivalence point occurs at 100.0 mL of KOH. mmol OH− added = 100.00 mL ×
0.100 M = 10.0 mmol OH−; as before, let the added OH− react to completion with the weak
acid; then see what is in solution after this reaction.

After 0 0 10.0 mmol
As expected at the equivalence point, enough OH− has been added to exactly neutralize all
the weak acid present initially. All that remains that affects the pH at the equivalence point
is the conjugate base of the weak acid (CN−). This is a weak base equilibrium problem.
1.0 × 10 −14
⇌
Kw
CN− + H2O HCN + OH− Kb = =
Kb 6.2 × 10 −10
Initial 10.0 mmol/200.0 mL 0 0 Kb = 1.6 × 10−5
−
x mol/L CN reacts with H2O to reach equilibrium
Equil. 0.0500 − x x x
x2 x2
Kb = 1.6 × 10−5 = ≈ , x = [OH−] = 8.9 × 10−4 M
0.0500 − x 0.0500
e. mmol OH− added = 125.0 mL × 0.100 M = 12.5 mmol OH−

After the titration reaction, we have a solution containing excess OH− and a weak base
CN−. When a strong base and a weak base are both present, assume that the amount of
OH− added from the weak base will be minimal; that is, the pH past the equivalence point
is determined by the amount of excess strong base.
2.5 mmol
[OH−]excess = = 0.011 M; pOH = 1.96; pH = 12.04
100.0 mL + 125.0 mL
167. This is a weak base (HONH2) titrated by a strong acid (HCl). To calculate the pH at the
various points, let the strong acid react completely with the weak base present; then see what
is in solution.
a. Only a weak base is present. Solve the weak base equilibrium problem.
HONH2 + H2O ⇌ HONH3+ + OH−

Equil. 0.200 - x x x
x2 x2
Kb = 1.1 × 10−8 = ≈ , x = [OH−] = 4.7 × 10−5 M
0.200 − x 0.200
0.200 mmol HONH 2

b. mmol HONH2 present = 100.0 mL × = 20.0 mmol HONH2
mL
0.100 mmol H +
mL
A buffer solution results after the titration reaction. Solving using the Henderson-
[base] K 1.0 × 10 −14
pH = pKa + log ; Ka = w = = 9.1 × 10−7
[acid] Kb 1.1 × 10 −8
 17.5 mmol/VT 
pH = −log(9.1 × 10−7) + log  , where VT = total volume, cancels.
 2.50 mmol/VT 
pH = 6.04 + log(7.00) = 6.04 + 0.845 = 6.89
A buffer solution results.
[base]  13.0 mmol/VT 

pH = pKa + log = 6.04 + log   = 6.04 + (0.269) = 6.31
[acid]  7.00 mmol/VT 
d. The equivalence point occurs at 200.0 mL of HCl added. mmol H+ added = 200.0 mL ×
0.100 M = 20.0 mmol H+
After 0 0 20.0 mmol
As is always the case in a weak base-strong acid titration, the pH at the equivalence point
is acidic because only a weak acid (HONH3+) is present. Solving the weak acid
equilibrium problem:
HONH3+ ⇌ H+ + HONH2
Initial 20.0 mmol/300.0 mL 0 0
Equil. 0.0667 − x x x
x2 x2
Ka = 9.1 × 10−7 = ≈ , x = [H+] = 2.5 × 10−4 M
0.0667 − x 0.0667

Two acids are present past the equivalence point, but the excess H+ will determine the pH
of the solution since HONH3+ is a weak acid.
10.0 mmol
[H+]excess = = 0.0250 M; pH = 1.602
100.0 mL + 300.0 mL
f. Notice that the pKa value for HONH3+ is equal to 6.04. This question is asking when does
pH = pKa. For a weak base-strong acid titration, this always occurs at the halfway point
to equivalence, where [HONH3+] = [HONH2]. It takes 200.0 mL of HCl to reach the
equivalence point, so it will take 100.0 mL of HCl to reach the halfway point to
equivalence where pH = pKa =6.04.
168. Titration i is a weak base titrated by a strong acid. The pH starts out basic because a weak base
is present. The pH drops as HCl is added; then at the halfway point to equivalence, pH = pKa.
Because Kb = 1.8 × 10 −5 for NH3, NH4+ has Ka = Kw/Kb = 5.6 × 10 −10 and pKa = 9.25. So, at
the halfway point to equivalence for this weak base-strong acid titration, pH = 9.25. The pH
continues to drop as HCl is added; then at the equivalence point the pH is acidic (pH < 7.00)
because the only important major species present is a weak acid (the conjugate acid of the weak
base). Past the equivalence point the pH becomes more acidic as excess HCl is added. Titration
ii is a strong acid titrated by a strong base. The pH is very acidic until just before the equivalence
point; at the equivalence point, pH = 7.00, and past the equivalence the pH is very basic.
Titrations iii and iv are weak acids titrated by strong bases. In a weak acid-strong base titration,
the pH starts off acidic, but not nearly as acidic as the strong acid titration (ii). The pH increases
as NaOH is added; then at the halfway point to equivalence, pH = pKa. The pH continues to
increase past the halfway point; then at the equivalence point the pH is basic (pH > 7.0). This
is because the only important major species present is a weak base (the conjugate base of the
weak acid). Past the equivalence point the pH becomes more basic as excess NaOH is added.
a. The strong acid titration has the lowest pH at the halfway point to equivalence. As
discussed above, its pH will be very acidic. For the weak acid titrations, pH = pKa at the
halfway point. For the HOCl titration, pH = −log(3.5 × 10−8) = 7.46 and for the HF titration,
pH = pKa = −log (7.2 × 10−4) = 3.14. For the weak base titration, pH = pKa = 9.25. The
correct order of increasing pH at the halfway point is ii < iv < iii < i.
b. The strong acid-strong base titration has pH = 7.00 at the equivalence point. The weak base
titration has an acidic pH at the equivalence point, and the weak acid titrations have basic
equivalence point pH values. Because HOCl is a weaker acid than HF, OCl− will be a
stronger conjugate base than F−. This results in the HOCl titration having a higher, more
basic pH at the equivalence point. The correct order of increasing pH at the equivalence
point is i < ii < iv < iii.
c. All require the same volume of titrant to reach the equivalence point. At the equivalence
point for all these titrations, moles acid = moles base (MAVA = MBVB). Because all the
molarities and volumes are the same in the titrations, the volume of titrant will be the same
(150.0 mL titrant added to reach the equivalence point).
169. Ca3(PO4)2(s) ⇌ 3 Ca2+(aq) + 2 PO43− (aq) Ksp = [Ca2+]3[PO43−]2

s mol/L of Ca3(PO4)2(s) dissolves to reach equilibrium
Equil. 3s 2s
Ksp = (3s)3(2s)2 = 108s5 ; Ksp = 108(1.6 × 10 −7 )5 = 1.1 × 10 −32
170. a. AgCl(s) ⇌ Ag+(aq) + Cl−(aq)

Equil. s s
Ksp = 1.6 × 10 −10 = [Ag+][Cl−] = s2, s = 1.3 × 10 −5 mol/L
b. Ag2S(s) ⇌ 2 Ag+(aq) + S2− (aq)

Equil. 2s s
Ksp = 1.6 × 10 −49 = [Ag+]2[S2−] = (2s)2s = 4s3, s = 3.4 × 10 −17 mol/L
c. CaF2(s) ⇌ Ca2+(aq) + 2 F−(aq)

Equil. s 2s
Ksp = 4.0 × 10 −11 = [Ca2+][F−]2 = s(2s)2 = 4s3, s = 2.2 × 10 −4 mol/L
d. CuS(s) ⇌ Cu2+(aq) + S2−(aq)

Equil. s s
Ksp = 8.5 × 10 −45 = [Cu2+][S2−] = s2, s = 9.2 × 10 −23 mol/L
The solubility order from least to most soluble is CuS < Ag2S < AgCl < CaF2.
171. PbI2(s) ⇌ Pb2+(aq) + 2 I−(aq) Ksp = 1.4 × 10 −8

Equil. s 0.048 + 2s
1.4 × 10−8 = (s)(0.048 + 2s)2 ≈ (s)(0.048)2, s = 6.1 × 10−6 mol/L; assumption good.
172. Pb(IO3)2(s) ⇌ Pb2+(aq) + 2 IO3−(aq)

Equil. s 0.072 + 2s
Ksp = [Pb2+][IO3−]2 = (s)(0.072 + 2s)2
From the problem, s = 6.0 × 10−9 mol/L; solving for Ksp:
Ksp = (6.0 × 10−9)[0.072 + 2(6.0 × 10−9)]2 = 3.1 × 10−11
173. 50.0 mL × 0.0413 M = 2.07 mmol Ag+; 50.0 mL × 0.100 M = 5.00 mmol IO3−
From the small Ksp value, assume AgIO3(s) precipitates completely. After reaction, 0 mmol
of Ag+ and 5.00 – 2.07 = 2.93 mmol IO3− remains. Now, let some AgIO3(s) dissolve in
solution with excess IO3− present to reach equilibrium.
AgIO3(s) ⇌ Ag+(aq) + IO3−(aq)

2.93 mmol
Initial 0 = 0.0293 M
100.0 mL
s mol/L AgIO3(s) dissolves to reach equilibrium
Equil. s 0.0293 + s
Ksp = [Ag+][IO3−], 3.17 × 10−8 = s(0.0293 + s) ≈ s(0.0293)
s = 1.08 × 10−6 mol/L = [Ag+]; assumption good.
174. From the problem, [Hg2+]0 = 0.088 M and [I−]0 = 5.0 M. Because the K values are large,
assume all reactions go to completion, and then solve an equilibrium problem.
Hg2+(aq) + 4 I−(aq) ⇌ HgI42−(aq) K = K1K2K3K4 = 1.0 × 1030

Before 0.088M 5.0 M 0
Change −0.088 −4(0.088) +0.088
After 0 4.6 M 0.088 M Assume reacts completely.
Equil. x 4.6 + 4x 0.088 − x
2−
[HgI 4 ] 0.088 − x 0.088
K = 1.0 × 10 30 = 2+ − 4
= ≈
[Hg ][I ] x (4.6 + 4 x) 4
x (4.6) 4
x = [Hg2+] = 2.0 × 10 −34 M; assumptions good. [I−] = 4.6 M; [HgI42−] = 0.088 M
a. [HgI42−] = 0.088 M b. [I−] = 4.6 M c. [Hg2+] = 2.0 × 10 −34 M
Challenge Problems
0.750 mmol
175. mmol HC3H5O2 present initially = 45.0 mL × = 33.8 mmol HC3H5O2
mL
0.700 mmol
mmol C3H5O2− present initially = 55.0 mL × = 38.5 mmol C3H5O2−
mL
The initial pH of the buffer is:
38.5 mmol
−
[C H O ] 100.0 mL 38.5
pH = pKa + log 3 5 2 = −log(1.3 × 10−5) + log = 4.89 + log = 4.95
[HC3 H 5 O 2 ] 33. 8 mmol 33.8
100.0 mL
Note: Because the buffer components are in the same volume of solution, we can use the mole
(or millimole) ratio in the Henderson-Hasselbalch equation to solve for pH instead of using the
concentration ratio of [C3H5O2−]/[HC3H5O2]. The total volume always cancels for buffer
solutions.
When NaOH is added, the pH will increase, and the added OH− will convert HC3H5O2 into
C3H5O2−. The pH after addition of OH− increases by 2.5%, so the resulting pH is:
4.95 + 0.025(4.95) = 5.07
At this pH, a buffer solution still exists, and the millimole ratio between C3H5O2− and
HC3H5O2 is:
− −
mmol C 3 H 5 O 2 mmol C 3 H 5 O 2
pH = pKa + log , 5.07 = 4.89 + log
mmol HC3 H 5 O 2 mmol HC3 H 5 O 2
−
mmol C 3 H 5 O 2
= 100.18 = 1.5
mmol HC3 H 5 O 2
Let x = mmol OH− added to increase pH to 5.07. Because OH− will essentially react to
completion with HC3H5O2, the setup to the problem using millimoles is:
HC3H5O2 + OH− → C3H5O2−

Before 33.8 mmol x mmol 38.5 mmol
After 33.8 − x 0 38.5 + x
−
mmol C 3 H 5 O 2 38.5 + x
= 1.5 = , 1.5(33.8 − x) = 38.5 + x, x = 4.9 mmol OH− added
mmol HC3 H 5 O 2 33.8 − x
The volume of NaOH necessary to raise the pH by 2.5% is:
1 mL
4.9 mmol NaOH × = 49 mL
0.10 mmol NaOH
49 mL of 0.10 M NaOH must be added to increase the pH by 2.5%.
176. For HOCl, Ka = 3.5 × 10−8 and pKa = −log(3.5 × 10−8) = 7.46. This will be a buffer solution
because the pH is close to the pKa value.
[OCl − ] [OCl − ] [OCl − ]
pH = pKa + log , 8.00 = 7.46 + log , = 100.54 = 3.5
[HOCl] [HOCl] [HOCl]
1.00 L × 0.0500 M = 0.0500 mol HOCl initially. Added OH− converts HOCl into OCl−. The
total moles of OCl− and HOCl must equal 0.0500 mol. Solving where n = moles:
nOCl − + nHOCl = 0.0500 and nOCl − = (3.5)nHOCl
(4.5)nHOCl = 0.0500, nHOCl = 0.011 mol; nOCl − = 0.039 mol
Need to add 0.039 mol NaOH to produce 0.039 mol OCl−.
0.039 mol = V × 0.0100 M, V = 3.9 L NaOH; note: Normal buffer assumptions hold.
177. a. Best acid will react with the best base present, so the dominate equilibrium is:
K a , NH
NH4+ + X− ⇌ NH3 + HX
[ NH 3 ][HX] +
Keq = + −
= 4
[ NH 4 ][X ] K a , HX
Because initially [NH4+]0 = [X−]0 and [NH3]0 = [HX]0 = 0, at equilibrium [NH4+] = [X−]
and [NH3] = [HX]. Therefore:
K a , NH + [HX]2
Keq = 4
= − 2
K a , HX [X ]
[H + ][X − ] [HX] [H + ]
The Ka expression for HX is: K a , HX = , =
[HX] [X − ] K a , HX
2
K a , NH + [HX]2  [H + ] 
Substituting into the Keq expression: Keq = 4
= − 2 = 
K a , HX [X ]  K a , HX 
 
Rearranging: [H+]2 = K a , NH + × K a , HX , or taking the −log of both sides:
4
pK a , NH + + pK a , HX
4
pH =
2
b. Ammonium formate = NH4(HCO2)
1.0 × 10 −14
K a , NH + = = 5.6 × 10−10, pKa = 9.25; K a , HCO 2 H = 1.8 × 10−4, pKa = 3.74
4
1.8 × 10 −5
pK a , NH 4 + + pK a , HCO 2 H 9.25 + 3.74
pH = = = 6.50
2 2
Ammonium acetate = NH4(C2H3O2); K a , HC 2 H 3O 2 = 1.8 × 10−5; pKa = 4.74
9.25 + 4.74
pH = = 7.00
2
Ammonium bicarbonate = NH4(HCO3); K a , H 2 CO3 = 4.3 × 10−7; pKa = 6.37
9.25 + 6.37
pH = = 7.81
2
c. NH4+(aq) + OH−(aq) → NH3(aq) + H2O(l); C2H3O2−(aq) + H+(aq) → HC2H3O2(aq)
178. a. Major species: H+, HSO4−, H2C6H6O6, and H2O; HSO4− is the best acid, with H2O as
the best base.
HSO4− ⇌ H+ + SO42−
Initial 0.050 M 0.050 M 0
Equil. 0.050 − x 0.050 + x x
(0.050 + x)( x)
= 1.2 × 10−2; we must use the quadratic equation.
(0.050 − x)
x = 8.5 × 10−3 M, [H+] = 0.050 + (8.5 × 10−3) = 5.85 × 10−2 M, pH = 1.23
b. Major species: H+, HSO4−, H2C6H6O6, OH−, Na+, H2O

5.0 mmol 5.0 mmol 20. mmol 10. mmol
React OH− to completion. React the best base with the best acid.
H+ + OH− → H2O
Before 5.0 10. –
After 0 5 –
HSO4− + OH− → H2O + SO42−

Before 5.0 5 – 0
After 0 0 – 5.0 mmol
After we have let OH− react to completion, the best acid remaining is H2C6H6O6, and the
best base remaining is SO42−. React these two together.
H2C6H6O6 + SO42− ⇌ HC6H6O6− + HSO4−

Initial 20./200. 5.0 mmol/200. mL 0 0
Change –x –x → +x +x
Equil. 0.10 – x 0.025 – x x x
K a1 , H 2 C 6 H 6 O 6 x2
K= = 6.6 × 10−3; = 6.6 × 10−3
K a 2 , H 2SO 4 (0.10 − x)(0.025 − x)
Using the quadratic equation, x = 3.7 × 10−3 M.
Use either K a1 for H2C6H6O6 or K a 2 for H2SO4 to calculate [H+].

−
[H + ][HC 6 H 6 O 6 ] [H + ] (0.0037)
For example, 7.9 × 10−5 = =
[H 2 C 6 H 6 O 6 ] (0.10 − 0.0037)
[H+] = 2.1 × 10−3 M, pH = 2.68
c. Major species: H+, HSO4−, H2C6H6O6, OH−, Na+, H2O

React OH− to completion first. React the best acid with the best base.
H+ + OH− → H2O
Before 5.0 30. –
After 0 25 –
HSO4− + OH− → H2O + SO42−

Before 5.0 25 – 0
After 0 20. – 5.0
H2C6H6O6 + OH− ⇌ HC6H6O6− + H2O

Before 20. 20. 0 –
After 0 0 20. –
After we let all of the OH− react completely, the major species are:
HC6H6O6−, SO42−, H2O, Na+

20. mmol 5.0 mmol
HC6H6O6− is the best acid as well as the best base present (amphoteric species).
Dominant reaction: HC6H6O6− + HC6H6O6− ⇌ H2C6H6O6 + C6H6O62−

pK a 1 + pK a 2 4.10 + 11.80
pH = = = 7.95
2 2
d. Major species: H+, HSO4−, H2C6H6O6, OH−, Na+, H2O
React OH− first to completion. React the best acid with the best base.
H+ + OH− → H2O
Before 5.0 50. –
After 0 45 –
HSO4− + OH− → H2O + SO42−

Before 5.0 45 – 0
After 0 40. – 5.0
H2C6H6O6 + OH− → H2O + HC6H6O6−

Before 20. 40. – 0
After 0 20. – 20.
HC6H6O6− + OH− → C6H6O62− + H2O

Before 20. 20. 0
After 0 0 20. mmol
After all the OH− reacts completely, we have a solution of the weak base C6H6O62−
(SO42− is a much weaker base than C6H6O62−, so we can ignore it). Solving the weak
base problem.
C6H6O62− + H2O ⇌ HC6H6O6− + OH−

Initial 20. mmol/600. mL 0 0
Kw x2
Kb = = 6.3 × 10−3 =
Ka 2 0.033 − x
Using the quadratic equation: x = [OH−] = 1.2 × 10−2 M; pOH = 1.92, pH = 12.08
179. a. CuBr(s) ⇌ Cu+ + Br− Ksp = 1.0 × 10−5

Cu + 3 CN−
+
⇌ Cu(CN)32− Kf = 1.0 × 1011
CuBr(s) + 3 CN ⇌ Cu(CN)32− + Br− K = 1.0 × 106
Because K is large, assume that enough CuBr(s) dissolves to completely use up the 1.0 M
CN−; then solve the back equilibrium problem to determine the equilibrium
concentrations.
CuBr(s) + 3 CN− ⇌ Cu(CN)32− + Br−

Before x 1.0 M 0 0
x mol/L of CuBr(s) dissolves to react completely with 1.0 M CN−
Change −x −3x → +x +x
After 0 1.0 − 3x x x
For reaction to go to completion, 1.0 − 3x = 0 and x = 0.33 mol/L. Now solve the back
equilibrium problem.
CuBr(s) + 3 CN− ⇌ Cu(CN)32− + Br−

Initial 0 0.33 M 0.33 M
2−
Let y mol/L of Cu(CN)3 react to reach equilibrium.
Change +3y ← −y −y
Equil. 3y 0.33 − y 0.33 − y
(0.33 − y ) 2 (0.33) 2
K = 1.0 × 106 = ≈ , y = 1.6 × 10−3 M; assumptions good.
(3y) 3 27 y 3
Of the initial 1.0 M CN−, only 3(1.6 × 10−3) = 4.8 × 10−3 M is present at equilibrium.
Indeed, enough CuBr(s) did dissolve to essentially remove the initial 1.0 M CN−.
This amount, 0.33 mol/L, is the solubility of CuBr(s) in 1.0 M NaCN.
b. [Br−] = 0.33 − y = 0.33 − 1.6 × 10−3 = 0.33 M
c. [CN−] = 3y = 3(1.6 × 10−3) = 4.8 × 10−3 M

180. Solubility in pure water:
CaC2O4(s) ⇌ Ca2+(aq) + C2O42−(aq) Ksp = 2 × 10−9

Equil. s s
Ksp = s2 = 2 × 10−9, s = solubility = 4.47 × 10−5 = 4 × 10−5 mol/L
Solubility in 0.10 M H+:
CaC2O4(s) ⇌ Ca2+ + C2O42− Ksp = 2 × 10−9

C2O42− + H+ ⇌ HC2O4− K = 1/ K a 2 = 1.6 × 104
HC2O4− + H+ ⇌ H2C2O4 K = 1/ K a1 = 15
CaC2O4(s) + 2 H+ ⇌ Ca2+ + H2C2O4 Koverall = 5 × 10−4

Initial 0.10 M 0 0
s mol/L of CaC2O4(s) dissolves to reach equilibrium
Equil. 0.10 – 2s s s
s2 s
5 × 10−4 = , = (5 × 10 − 4 )1/ 2 , s = 2 × 10 −3 mol / L
(0.10 − 2 s ) 2
0.10 − 2 s
Solubility in 0.10 M H + 2 × 10 −3 mol / L

= = 50
Solubility in pure water 4 × 10 −5 mol / L
CaC2O4(s) is 50 times more soluble in 0.10 M H+ than in pure water. This increase in
solubility is due to the weak base properties of C2O42−.
181. a. SrF2(s) ⇌ Sr2+(aq) + 2 F−(aq)

Initial 0 0
s mol/L SrF2 dissolves to reach equilibrium
Equil. s 2s
[Sr2+][F−]2 = Ksp = 7.9 × 10−10 = 4s3, s = 5.8 × 10−4 mol/L in pure water
b. Greater, because some of the F− would react with water:
F− + H2O ⇌ HF + OH−
Kw
Kb = = 1.4 × 10−11
K a , HF
This lowers the concentration of F−, forcing more SrF2 to dissolve.
c. SrF2(s) ⇌ Sr2+ + 2 F− Ksp = 7.9 × 10−10 = [Sr2+][F−]2
Let s = solubility = [Sr2+]; then 2s = total F− concentration.
Since F− is a weak base, some of the F− is converted into HF. Therefore:

total F− concentration = 2s = [F−] + [HF]

[H + ][F − ] 1.0 × 10 −2 [F − ]
HF ⇌ H+ + F− Ka = 7.2 × 10−4 = = (since pH = 2.00 buffer)
[HF] [HF]
[F − ]
7.2 × 10−2 = , [HF] = 14[F−]; Solving:
[HF]
[Sr2+] = s; 2s = [F−] + [HF] = [F−] + 14[F−], 2s = 15[F−], [F−] = 2s/15
2
 2s 
Ksp = 7.9 × 10−10 = [Sr2+][F−]2 = (s)   , s = 3.5 × 10−3 mol/L in pH = 2.00 solution
 15 
182. Ksp = [Ni2+][S2−] = 3 × 10 −21
H2S(aq) ⇌ H+(aq) + HS−(aq) K a1 = 1.0 × 10-7

HS−(aq) ⇌ H+(aq) + S2−(aq) K a 2 = 1 × 10 −19
[H + ] 2 [S 2− ]
H2S(aq) ⇌ 2 H+(aq) + S2−(aq) K = K a1 × K a 2 = 1 × 10 −26 =
[H 2 S]
Because K is very small, only a tiny fraction of the H2S will react. At equilibrium, [H2S]
= 0.10 M and [H+] = 1 × 10 −3 .
K[H 2S] (1 × 10 −26 )(0.10)
[S2−] = + 2
= −3 2
= 1 × 10 −21 M
[H ] (1 × 10 )
NiS(s) ⇌ Ni2+(aq) + S2−(aq) Ksp = 3.0 × 10 −21
Precipitation of NiS will occur when Q > Ksp. We will calculate [Ni2+] for Q = Ksp.
3.0 × 10 −21
Q = Ksp = [Ni2+][S2−] = 3.0 × 10 −21 , [Ni2+] = = 3 M = maximum concentration
1 × 10 − 21
183. We need to determine [S2−]0 that will cause precipitation of CuS(s) but not MnS(s).
For CuS(s):
CuS(s) ⇌ Cu2+(aq) + S2−(aq) Ksp = [Cu2+][S2−] = 8.5 × 10 −45

K sp 8.5 × 10 −45
[Cu2+]0 = 1.0 × 10 −3 M, 2+
= −3
= 8.5 × 10 −42 M = [S2− ]
[Cu ]0 1.0 × 10
This [S2−] represents the concentration that we must exceed to cause precipitation of CuS
because if [S2−]0 > 8.5 × 10−42 M, Q > Ksp.
For MnS(s):
MnS(s) ⇌ Mn2+(aq) + S2−(aq) Ksp = [Mn2+][ S2−] = 2.3 × 10 −13

K sp 2.3 × 10 −13
[Mn2+]0 = 1.0 × 10 −3 M, 2+
= −3
= 2.3 × 10 −10 M = [S2− ]
[Mn ] 1.0 × 10
This value of [S2−] represents the largest concentration of sulfide that can be present without
causing precipitation of MnS. That is, for this value of [S2−], Q = Ksp, and no precipitatation
of MnS occurs. However, for any [S2−]0 > 2.3 × 10 −10 M, MnS(s) will form.
We must have [S2−]0 > 8.5 × 10 −42 M to precipitate CuS, but [S2−]0 < 2.3 × 10 −10 M to prevent
precipitation of MnS.
The question asks for a pH that will precipitate CuS(s) but not MnS(s). We need to first
choose an initial concentration of S2− that will do this. Let’s choose [S2−]0 = 1.0 × 10 −10 M
because this will clearly cause CuS(s) to precipitate but is still less than the [S2−]0 required for
MnS(s) to precipitate. The problem now is to determine the pH necessary for a 0.1 M H2S
solution to have [S2−] = 1.0 × 10 −10 M. Let’s combine the K a1 and K a 2 equations for H2S to
determine the required [H+].
H2S(aq) ⇌ H+(aq) + HS−(aq) K a1 = 1.0 × 10 −7

HS−(aq) ⇌ H+(aq) + S2−(aq) K a 2 = 1 × 10 −19
H2S(aq) ⇌ 2H+(aq) + S2−(aq) K = K a1 × K a 2 = 1.0 × 10 −26
[H + ]2 [S2− ] [H + ]2 (1 × 10 −10 )
1 × 10 − 26 = = , [H + ] = 3 × 10 −9 M
[H 2S] 0.10
pH = − log(3 × 10 −9 ) = 8.5. So, if pH = 8.5, [S2− ] = 1 × 10 −10 M, which will cause

precipitation of CuS(s) but not MnS(s).
Note: Any pH less than 8.7 would be a correct answer to this problem.
184. Major species: H+, HSO4−, Ba2+, NO3−, and H2O; Ba2+ will react with the SO42− produced
from the Ka reaction for HSO4−.
HSO4− ⇌ H+ + SO42− K a 2 = 1.2 × 10−2

Ba2+ + SO4 ⇌
2−
BaSO4(s) K = 1/Ksp = 1/(1.5 × 10−9) = 6.7 × 108
Ba2+ + HSO4− ⇌ H+ + BaSO4(s) Koverall = (1.2 × 10−2) × (6.7 × 108) = 8.0 × 106
Because Koverall is so large, the reaction essentially goes to completion. Because H2SO4 is a
strong acid, [HSO4−]0 = [H+]0 = 0.10 M.
Ba2+ + HSO4− ⇌ H+ + BaSO4(s)

Before 0.30 M 0.10 M 0.10 M
Change −0.10 −0.10 → +0.10
After 0.20 0 0.20 M New initial
Change +x +x −x
Equil. 0.20 + x x 0.20 − x
0.20 − x 0.20
K = 8.0 × 106 = ≈ , x = 1.3 × 10−7 M; assumptions good.
(0.20 + x) x 0.20( x)
[H+] = 0.20 − 1.3 × 10−7 = 0.20 M; pH = −log(0.20) = 0.70
[Ba2+] = 0.20 + 1.3 × 10−7 = 0.20 M
From the initial reaction essentially going to completion, 1.0 L(0.10 mol HSO4−/L) =
0.10 mol HSO4− reacted; this will produce 0.10 mol BaSO4(s). Only 1.3 × 10−7 mol
of this dissolves to reach equilibrium, so 0.10 mol BaSO4(s) is produced.
233.4 g BaSO 4
0.10 mol BaSO4 × = 23 g BaSO4 produced
mol
185. AgCN(s) ⇌ Ag+(aq) + CN−(aq) Ksp = 2.2 × 10 −12

H+(aq) + CN−(aq) ⇌ HCN(aq) K = 1/K a, HCN = 1.6 × 109
AgCN(s) + H+(aq) ⇌ Ag+(aq) + HCN(aq) K = 2.2 × 10 −12 (1.6 × 109 ) = 3.5 × 10 −3
AgCN(s) + H+(aq) ⇌ Ag+(aq) + HCN(aq)

Initial 1.0 M 0 0
s mol/L AgCN(s) dissolves to reach equilibrium
Equil. 1.0 − s s s
[Ag + ][HCN] s(s) s2
3.5 × 10 −3 = = ≈ , s = 5.9 × 10 −2
[H + ] 1.0 − s 1.0
Assumption fails the 5% rule (s is 5.9% of 1.0 M). Using the method of successive
approximations:
s2
3.5 × 10 −3 = , s = 5.7 × 10 − 2
1.0 − 0.059
s2
3.5 × 10 −3 = , s = 5.7 × 10 − 2 (consistent answer)
1.0 − 0.057
The molar solubility of AgCN(s) in 1.0 M H+ is 5.7 × 10 −2 mol/L.
186. a. HA ⇌ H+ + A− Ka = 5.0 × 10−10; [HA]0 = 1.00 × 10−4 M
Because this is a dilute solution of a very weak acid, H2O cannot be ignored as a source
of H+.
From Section 7.9 of text, try: [H+] = (Ka[HA]0 + Kw)1/2 = 2.4 × 10−7 M; pH = 6.62
Check assumption:
[ H + ]2 − K w
= 2.0 × 10−7 << 1.0 × 10−-4; assumption good. pH = 6.62
[H + ]
b. 100.0 mL × (1.00 × 10−4 mmol/mL) = 1.00 × 10−2 mmol HA
5.00 mL × (1.00 × 10−3 mmol/mL) = 5.00 × 10−3 mmol NaOH added; let OH− react
completely with HA. After reaction, 5.0 × 10−3 mmol HA and 5.00 × 10−3 mmol A− are
in 105.0 mL. [A−]0 = [HA]0 = 5.00 × 10−3 mmol/105.0 mL = 4.76 × 10−5 M
A− + H2O ⇌ HA + OH− Kb = Kw/Ka = 2.0 × 10−5

Initial 4.76 × 10−5 M −5
4.76 × 10 M 0
Equil. 4.76 × 10−5 − x 4.76 × 10−5 + x x
(4.76 × 10 −5 + x) x
Kb = 2.0 × 10−5 = −5
; x will not be small compared to 4.76 × 10−5.
(4.76 × 10 − x)
Using the quadratic formula and carrying extra sig. figs.:
x2 + (6.76 × 10−5)x − 9.52 × 10−10 = 0
x = [OH−] = 1.2 × 10−5 M; pOH = 4.92; pH = 9.08
c. At the stoichiometric point, all the HA is converted into A−.
A− + H2O ⇌ HA + OH− Kb = 2.0 × 10−5

0.0100 mmol
Initial = 9.09 × 10−5 M 0 0
110.0 mL
Equil. 9.09 × 10−5 − x x x
x2 x2
Kb = 2.0 × 10−5 = ≈ , x = 4.3 × 10−5; assumption poor.
(9.09 × 10 −5 − x) 9.09 × 10 −5
x2 + (2.0 × 10−5)x − (1.82 × 10−9) = 0, x = 3.4 × 10−5 M = [OH−]
pOH = 4.47; pH = 9.53; assumption to ignore H2O contribution to OH− is good.
187. a. 200.0 mL × 0.250 mmol Na3PO4/mL = 50.0 mmol Na3PO4
135.0 mL × 1.000 mmol HCl/mL = 135.0 mmol HCl
100.0 mL × 0.100 mmol NaCN/mL = 10.0 mmol NaCN
Let H+ from the HCl react to completion with the bases in solution. In general, react the
strongest base first and so on. Here, 110.0 mmol of HCl reacts to convert all CN− to HCN
and all PO43− to H2PO4−. At this point 10.0 mmol HCN, 50.0 mmol H2PO4−, and 25.0 mmol
HCl are in solution. The remaining HCl reacts completely with H2PO4−, converting 25.0
mmol to H3PO4. The final solution contains 25.0 mmol H3PO4, (50.0 − 25.0 =) 25.0 mmol
H2PO4−, and 10.0 mmol HCN. HCN (Ka = 6.2 × 10−10) is a much weaker acid than either
H3PO4 ( K a1 = 7.5 × 10−3) or H2PO4− ( K a 2 = 6.2 × 10−8), so ignore it. We have a buffer
solution. Principal equilibrium reaction is:
H3PO4 ⇌ H+ + H2PO4− K a1 = 7.5 × 10−3

Initial 25.0 mmol/435.0 mL 0 25.0/435.0
Equil. 0.0575 − x x 0.0575 + x
x(0.0575 + x)
K a1 = 7.5 × 10−3 = ; normal assumptions don't hold here.
0.0575 − x
x2 + (0.0650)x − 4.31 × 10−4 = 0, x = 0.0061 M = [H+]; pH = 2.21

10.0 mmol
b. [HCN] = = 2.30 × 10−2 M; HCN dissociation will be minimal.
435.0 mL
188. 50.0 mL × 0.100 M = 5.00 mmol H2SO4; 30.0 mL × 0.100 M = 3.00 mmol HOCl
25.0 mL × 0.200 M = 5.00 mmol NaOH; 10.0 mL × 0.150 M = 1.50 mmol KOH
25.0 mL × 0.100 M = 2.50 mmol Ba(OH)2 = 5.00 mmol OH−; we've added 11.50 mmol OH−
total.
Let OH− react completely with the best acid present (H2SO4).
10.00 mmol OH− + 5.00 mmol H2SO4 → 10.00 mmol H2O + 5.00 mmol SO42−
OH− still remains after reacting completely with H2SO4. OH− will then react with the next
best acid (HOCl). The remaining 1.50 mmol OH− will convert 1.50 mmol HOCl into 1.50
mmol OCl−, resulting in a solution with 1.50 mmol OCl− and (3.00 − 1.50 =) 1.50 mmol
HOCl. The major species at this point are HOCl, OCl−, SO42−, and H2O plus cations that
don't affect pH. SO42− is an extremely weak base (Kb = 8.3 × 10−13). We have a buffer
solution composed of HOCl and OCl−. Because [HOCl] = [OCl−]:
[H+] = Ka = 3.5 × 10−8 M; pH = 7.46; assumptions good.
189. Major species PO43−, H+, HSO4−, H2O, and Na+; let the best base (PO43−) react with the best
acid (H+). Assume the reaction goes to completion because H+ is reacting. Note that the
concentrations are halved when equal volumes of the two reagents are mixed.
PO43− + H+ → HPO42−
Before 0.25 M 0.050 M 0
After 0.20 M 0 0.050 M
Major species: PO43−, HPO42−, HSO4−, H2O, and Na+; react the best base (PO43−) with the
best acid (HSO4−). Because K for this reaction is very large, assume the reaction goes to
completion.
K a , HSO −
PO43− + HSO4− → HPO42− + SO42− K= 4
= 2.5 × 1010
K a , HPO 2−
4
Before 0.20 M 0.050 M 0.050 M 0

After 0.15 M 0 0.100 M 0.050 M
Major species: PO43−, HPO42−, SO42− (a very weak base with Kb = 8.3 × 10−13), H2O, and
Na+; because the best base present (PO43−) and best acid present (HPO42−) are conjugate acid-
base pairs, a buffer solution exists. Because Kb for PO43− is a relatively large value (Kb =
K w /K a, HPO 2− = 0.021), the usual assumptions that the amount of base that reacts to each
4
equilibrium is negligible compared with the initial concentration of base will not hold. Solving
using the Kb reaction for PO43−:
PO43− + H2O ⇌ HPO42− + OH− Kb = 0.021

Initial 0.15 M 0.100 M 0
Equil. 0.15 − x 0.100 + x x
(0.100 + x)( x)
Kb = 0.021 = ; using quadratic equation:
0.15 − x
x = [OH−] = 0.022 M; pOH = 1.66; pH = 12.34
190. a. At the third halfway point, pH = pK a 3 = −log(4.8 × 10−13) = 12.32.
b. At third equivalence point, the reaction is:
PO43− + H2O ⇌ HPO42− + OH−

10. mmol Kw 1.0 × 10 −14
Initial – 0 0 Kb = =
400. mL K a3 4.8 × 10 −13
Change −x → +x +x Kb = 2.1 × 10−2
x2
= 2.1 × 10−2; using the quadratic equation:
0.025 − x
x = 1.5 × 10−2 M = [OH−]; pOH = 1.82; pH = 12.18
c. The pH at the third halfway point must be more acidic (lower pH) than the pH at the third
equivalence point. Therefore, the pH at the third halfway point cannot equal 12.32. In part
a we assumed that x was negligible:
HPO42− + H2O ⇌ PO43− + H3O+ K a 3 = 4.8 × 10−13

Initial 5.0 mmol/350. mL 5.0/350. 0
Change −x +x +x
Equil. 0.014 − x 0.014 + x x
(0.014 + x)( x) (0.014)( x)

≈ , x = 4.8 × 10−13 M
(0.014 − x) (0.014)
This looks fine, but this is a situation where we must use the Kb reaction for the weak base
PO43− to solve for the pH. The [OH−] in solution is not negligible compared to 0.014 M, so
the usual assumptions don’t hold here. The usual buffer assumptions don’t hold in very
acidic or very basic solutions. In this very basic solution, we must use the Kb reaction and
the quadratic equation:
PO43− + H2O ⇌ HPO42− + OH−
d. PO43− + H2O ⇌ HPO42− + OH− Kb = 2.1 × 10−2

Initial 0.014 M – 0.014 M 0
Change −x – +x +x
Equil. 0.014 − x – 0.014 + x x
(0.14 + x)( x)
= 2.1 × 10−2; using the quadratic equation:
(0.14 − x)
x = [OH−] = 7.0 × 10−3 M; pOH = 2.15; pH = 11.85
This pH answer makes more sense because it is below the pH at the third equivalence
point calculated in part b of this problem (pH = 12.18).
191. H3A: pK a1 = 3.00, pK a 2 = 7.30, pK a 3 = 11.70
The pH at the second stoichiometric point is:

pK a 2 + pK a 3 7.30 + 11.70
pH = = = 9.50
2 2
Thus to reach a pH of 9.50, we must go to the second stoichiometric point. 100.0 mL ×
0.0500 M = 5.00 mmol H3A initially. To reach the second stoichiometric point, we need 10.0
mmol OH− = 1.00 mmol/mL × VNaOH. Solving for VNaOH:
VNaOH = 10.0 mL (to reach pH = 9.50)
pH = 4.00 is between the first halfway point to equivalence (pH = pK a1 = 3.00) and the first
pK a1 + pK a 2
stoichiometric point (pH = = 5.15).
2
This is the buffer region controlled by H3A ⇌ H2A− + H+.

[H 2 A − ] [H A − ] [H 2 A − ]
pH = pK a1 + log , 4.00 = 3.00 + log 2 , = 10.
[H 3 A] [H 3 A] [H 3 A]
Because both species are in the same volume, the mole ratio also equals 10. Let n = mmol:
nH −
2A
= 10. and nH − + nH 3A = 5.00 mmol (mole balance)
2A
nH 3 A
11nH 3A = 5.00, n H 3A = 0.45 mmol; nH − = 4.55 mmol

2A
We need to add 4.55 mmol OH− to get 4.55 mmol H2A− from the original H3A present.
4.55 mmol = 1.00 mmol/mL × VNaOH, VNaOH = 4.55 mL of NaOH (to reach pH = 4.00)
Note: Normal buffer assumptions are good.
192. a. V1 corresponds to the titration reaction of CO32− + H+ → HCO3−; V2 corresponds to the

titration reaction of HCO3− + H+ → H2CO3.
Here, there are two sources of HCO3−: NaHCO3 and the titration of Na2CO3, so V2 > V1.
b. V1 corresponds to two titration reactions: OH− + H+ → H2O and CO32− + H+ → HCO3−.

V2 corresponds to just one titration reaction: HCO3− + H+ → H2CO3.
Here, V1 > V2 due to the presence of OH− , which is titrated in the V1 region.
c. 0.100 mmol HCl/mL × 18.9 mL = 1.89 mmol H+; Because the first stoichiometric point
only involves the titration of Na2CO3 by H+, 1.89 mmol of CO32− has been converted into
HCO3−. The sample contains 1.89 mmol Na2CO3 × 105.99 mg/mmol = 2.00 × 102 mg =
0.200 g Na2CO3.
The second stoichiometric point involves the titration of HCO3− by H+.

0.100 mmol H +
× 36.7 mL = 3.67 mmol H+ = 3.67 mmol HCO3−
mL
1.89 mmol NaHCO3 came from the first stoichiometric point of the Na2CO3 titration.
3.67 − 1.89 = 1.78 mmol HCO3− came from NaHCO3 in the original mixture.
1.78 mmol NaHCO3 × 84.01 mg NaHCO3/mmol = 1.50 × 102 mg NaHCO3 =

0.150 g NaHCO3
0.200 g
Mass % Na2CO3 = × 100 = 57.1% Na2CO3
(0.200 + 0.150) g
0.150 g
Mass % NaHCO3 = × 100 = 42.9% NaHCO3
0.350 g
Marathon Problems
193. Major species: PO43−, OH−, H+, CN−, Na+, K+, Cl−, H2O
5.00 mmol 5.00 mmol 15.0 mmol 7.50 mmol
PO43− and CN− are weak bases.

PO43− + H2O ⇌ HPO42− + OH− Kb = Kw/ K a 3 = 2.1 × 10−2
CN− + H2O ⇌ HCN + OH− Kb = Kw/Ka = 1.6 × 10−5

One of the keys to this problem is to recognize that pK a 2 for H3PO4 = 7.21 [−log(6.2 × 10−8)
= 7.21]. The K a 2 reaction for H3PO4 is:
H2PO4− ⇌ HPO42− + H+ K a 2 = 6.2 × 10−8; pK a 2 = 7.21
The pH of the final solution will equal 7.21 when we have a buffer solution where [H2PO4− ] =
[HPO42−]. To solve this problem, we need to determine the quantity of HNO3 that must be
added so that the final solution contains equal moles of H2PO4− and HPO42−.
To start the problem, let’s see what is in solution after we let the best acid and best base react
in a series of reactions. In each of the following reactions, something strong is reacting, so we
assume the reactions will go to completion. The first reaction to run to completion is the strong
acid reacting with the strong base: H+ + OH− → H2O.
H+ + OH− → H2O
After 10.0 mmol 0
After all of the strong base is neutralized, the next best base present is PO43−.
H+ + PO43− → HPO42−
The next best base present is CN−.
H+ + CN− → HCN
We need to add 2.5 mmol H+ to convert all the CN− into HCN; then all that remains is 5.00
mmol HPO42− and 7.5 mmol HCN (a very weak acid with Ka = 6.2 × 10−10). From here, we
would need to add another 2.5 mmol H+ in order to convert one-half of the HPO42− present
into its conjugate acid so that [HPO42−] = [H2PO4−] and pH = pK a 2 = 7.21. Adding 5.0 mmol
H+ to the original solution:
H+ + CN− → HCN
Before 5.0 mmol 2.5 mmol 5.0 mmol
H+ + HPO42− → H2PO4−
After 5.0 mmol H+ (HNO3) has been added to the original mixture, we have a final solution
containing equal moles of HPO42− and H2PO4− so that pH = pK a 2 = 7.21. Note that HCN,
with Ka = 6.2 × 10−10, is too weak of an acid to interfere with the H2PO4−/ HPO42− buffer.
1 mL
Volume HNO3 = 5.0 mmol HNO3 × = 50. mL HNO3
0.100 mmol HNO 3
194. a. In very acidic solutions, the reaction that occurs to increase the solubility is Al(OH)3(s) +
3H+ → Al3+(aq) + 3H2O(l). In very basic solutions, the reaction that occurs to increase
solubility is Al(OH)3(s) + OH−(aq) → Al(OH)4−(aq).
b. Al(OH)3(s) ⇌ Al3+ + 3 OH−; Al(OH)3(s) + OH- ⇌ Al(OH)4−
S = solubility = total Al3+ concentration = [Al3+] + [Al(OH)4−]

K sp [H + ]3
[Al3+] = = Ksp × , because [OH−]3 = (Kw/[H+])3
[OH − ]3 Kw
3
−
[Al(OH) 4 ] Kw KK w
= K; [OH−] = +
; [Al(OH)4−] = K[OH−] =
−
[OH ] [H ] [H + ]
S = [Al3+] + [Al(OH)4−] = [H+]3Ksp/Kw3 + KKw/[H+]
c. Ksp = 2 × 10−32; Kw = 1.0 × 10−14; K = 40.0

[H + ]3 (2 × 10 −32 ) 40.0 (1.0 × 10 −14 ) 4.0 × 10 −13
S= + = [H+ 3
] (2 × 10 10
) +
(1.0 × 10 −14 ) 3 [H + ] [H + ]
pH solubility (S, mol/L) log S

4.0 2 × 10−2 −1.7
5.0 2 × 10−5 −4.7
6.0 4.2 × 10−7 −6.38
7.0 4.0 × 10−6 −5.40
8.0 4.0 × 10−5 −4.40
9.0 4.0 × 10−4 −3.40
10.0 4.0 × 10−3 −2.40
11.0 4.0 × 10−2 −1.40
12.0 4.0 × 10−1 −0.40
As expected, the solubility of Al(OH)3(s) is increased by very acidic solutions and by

very basic solutions.

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CHAPTER 8

APPLICATIONS OF AQUEOUS EQUILIBRIA

H+(aq) + CO32−(aq) → HCO3−(aq); OH−(aq) + HCO3−(aq) → H2O(l) + CO32−(aq)

[base] [base]  [base] 

HOPr(aq) ⇌ H+(aq) + OPr−(aq) Ka = 1.3 × 10−5

b. This is a weak base problem.

x = [OH−] = 8.8 × 10−6 M; pOH = 5.06; pH = 8.94; assumptions good.

c. Pure H2O, [H+] = [OH−] = 1.0 × 10−7 M; pH = 7.00

HOPr(aq) ⇌ H+(aq) + OPr−(aq) Ka = 1.3 × 10−5

Alternately, we can use the Henderson-Hasselbalch equation to calculate the pH of buffer

HOPr ⇌ H+ + OPr− Ka = 1.3 × 10−5

b. Added H+ reacts completely with the best base present, OPr−.

d. Added H+ reacts completely with the best base present, OPr−.

HOPr + OH− → OPr- + H2O

[OH−] = 0.020 + x ≈ 0.020 M; pOH = 1.70; pH = 12.30; assumption good.

c. This is a strong base in water. [OH−] = 0.020 M; pOH = 1.70; pH = 12.30

HOPr + OH− → OPr− + H2O

Solution Initial pH After Added H+ After Added OH−

c. Bz− + H2O ⇌ HBz + OH−

pOH = 9.63; pH = 4.37

[F − ][H + ] (1.00 + x)( x) (1.00)( x)

x = [H+] = 0.60 × (7.2 × 10−4) = 4.3 × 10 −4 M; assumptions good.

pH = −log(4.3 × 10−4) = 3.37

[base]  1.0 × 10 −14  [HONH 2 ]

Initial 0.80 M 0.80 M 0

(0.80 + x)( x) (0.80)( x)

HONH3+ + OH− → HONH2 + H2O

A buffer solution results. Using the Henderson-Hasselbalch equation:

A buffer solution results after reaction. Using the Henderson-Hasselbalch equation:

31. Ka for H2NNH3+ = K w /K b, H 2 NNH 2 = 1.0 × 10−14/3.0 × 10−6 = 3.3 × 10−9

H2NNH3+ + OH− → H2NNH2 + H2O

We want mol H2NNH3+ = mol H2NNH2. So:

0.80 − x = 0.40 + x, 2x = 0.40, x = 0.20 mol OH−

We want mol HOCl = mol OCl−. Therefore:

0.90 − x = 0.20 + x, 2x = 0.70, x = 0.35 mol H+

pH = −log(4.3 × 10 −5 ) = 4.37; assumptions good.

Alternatively, we can use the Henderson-Hasselbalch equation to calculate the pH of buffer

We will use the Henderson-Hasselbalch equation to calculate the concentration ratio

[C2H3O2−] + [HC2H3O] = 2.0 M and [C2H3O2−] produced = [OH−] added

Because [C2H3O2−] + [HC2H3O2] = 2.0 M:

[C2H3O2−] = [HC2H3O2] = 1.0 M = [OH−] added

[C2H3O2−] = 0.18[HC2H3O2] or [HC2H3O2] = 5.6[C2H3O2−]

Because [C2H3O2−] + [HC2H3O2] = 2.0 M:

1.8[HC2H3O2] = [C2H3O2−] or [HC2H3O2] = 0.56[C2H3O2−]

1.56[C2H3O2−] = 2.0 M, [C2H3O2−] = 1.3 M = [OH−] added

[C2H3O2−] + [HC2H3O2] = 1.0 M and [HC2H3O2] = [H+] added

[C2H3O2−] = 0.29[HC2H3O2]; 0.29[HC2H3O2] + [HC2H3O2] = 1.0 M

[HC2H3O2] = 0.78 M = [H+] added

0.78 mol of HCl must be added to produce a solution with pH = 4.20.

[C2H3O2−] = 1.8[HC2H3O2]; 1.8[HC2H3O2] + [HC2H3O2] = 1.0 M

[HC2H3O2] = 0.36 M = [H+] added

0.36 mol of HCl must be added to produce a solution with pH = 5.00.

1 mol NaOH 1 mol OH − 0.10 mol

C6H5NH3+ + OH− → C6H5NH2 + H2O

a. 0.05 M CH3NH2 (no CH3NH3+ remains, no buffer)

6.3 × 10 −8 ([OCl − ] − 9.57 × 10 −8 )

HONH2 + H2O ⇌ HONH3+ + OH− Kb = 1.1 × 10−8

This expression holds if x is negligible as compared to [HONH3+]0 and [HONH2]0 as it was in

pH = −log(1.3 × 10−7) = 6.89