[ H 3O + ][ F ] ( x ) ( x ) x2
Ka 6.6 104 assuming x 0.500
[ HF] 0.500 x 0.500
Equation: HF(aq) + H 2 O(l) H 3 O + (aq) + F (aq)
Initial: 0.500 M 0.100 M 0M
Changes: x M +x M +x M
Equil: (0.500 x ) M (0.100+x) M xM
[ H 3O + ][ F ] ( x ) (0100
. + x) 0100
. x
Ka 6.6 104 assuming x 0.100
[HF] 0.500 x 0.500
6.6 104 0.500
x= = 3.3 103 M = F The assumption is valid.
0.100
HF = 0.500 M 0.003M = 0.497 M
[H3O+] = 0.100 M + x = 0.100 M + 0.003 M = 0.103 M
1B . 103 M in
From Example 17-6 in the text, we know that [ H 3O + ] [C 2 H 3O 2 ] 13
0.100 M HC 2 H 3O 2 . We base our calculation, as usual, on the balanced chemical
equation. The concentration of H 3O + from the added HCl is represented by x.
437
Chapter 17: Additional Aspects of Acid–Base Equilibria
Equation: HC 2 H 3 O 2 (aq) + H 2 O(l) +
H 3 O (aq) + C 2 H 3 O 2 (aq)
Initial: 0.100 M 0M 0M
Changes: 0.00010 M +0.00010 M +0.00010 M
From HCl: +x M
Equil: 0.100 M (0.00010 x) M 0.00010 M
2B This time, a solid sample of a weak base is being added to a solution of its conjugate
acid. We let x represent the concentration of acetate ion from the added sodium acetate.
Notice that sodium acetate is a strong electrolyte, thus, it completely dissociates in
aqueous solution. H 3O + = 10 pH = 10 5.00 = 1.0 10 5 M = 0.000010 M
Equation: HC 2 H 3 O 2 aq + H 2 O(l)
C 2 H 3 O 2 aq + H 3 O + aq
Initial: 0.100 M 0M 0M
Changes: 0.000010 M +0.000010 M +0.000010 M
From NaAc: +x M
Equil: 0.100 M (0.000010 + x) M 0.000010 M
438
Chapter 17: Additional Aspects of Acid–Base Equilibria
3B HCl dissociates essentially completely in water and serves as a source of hydronium ion.
This reacts with ammonia to form ammonium ion:
NH3 aq + H3O+ aq NH 4+ aq + H 2 O(l) .
Because a buffer contains approximately equal amounts of a weak base (NH3) and its
conjugate acid (NH4+), to prepare a buffer we simply add an amount of HCl equal to
approximately half the amount of NH3(aq) initially present.
4A We first find the formate ion concentration, remembering that NaCHO 2 is a strong
b g
electrolyte, existing in solution as Na + aq and CHO 2 aq .
23.1g NaCHO 2 1000 mL 1 mol NaCHO 2 1 mol CHO 2
[CHO 2 ] 0.679 M
500.0 mL soln 1L 68.01g NaCHO 2 1 mol NaCHO 2
As usual, the solution to the problem is organized around the balanced chemical equation.
Equation: HCHO 2 aq + H 2 O(l) CHO 2 aq + H 3 O aq
+
This gives H3O + = 1.14 104 M . The assumption that x 0.432 is clearly correct.
pH log H 3O log 1.14 104 3.94 3.9
439
Chapter 17: Additional Aspects of Acid–Base Equilibria
4B The concentrations of the components in the 100.0 mL of buffer solution are found via
the dilution factor. Remember that NaC2 H 3O 2 is a strong electrolyte, existing in
solution as
b g
Na + aq and C 2 H 3O 2 aq . b g
63.0 mL 37.0 mL
[HC 2 H 3 O 2 ] 0.200 M 0.126 M [C 2 H 3O 2 ] 0.200 M 0.0740 M
100.0 mL 100.0 mL
As usual, the solution to the problem is organized around the balanced chemical equation.
HC2 H 3O 2 aq + H 2 O(l) C2 H 3O 2 aq + H 3O aq
Equation: +
5A We know the initial concentration of NH 3 in the buffer solution and can use the pH to
find the equilibrium [OH-]. The rest of the solution is organized around the balanced
chemical equation. Our first goal is to determine the initial concentration of NH 4 .
pOH = 14.00 pH = 14.00 9.00 5.00 [OH ] 10 pOH 105.00 10
. 105 M
Equation: NH3 aq + H 2 O(l)
NH 4 + aq + OH aq
Initial: 0.35 M xM 0 M
Changes: 1.0 105 M 1.0 105 M 1.0 105 M
Equil: (0.35 1.0 105 ) M . 105 ) M
( x 10 . 105 M
10
[NH 4 ][OH ] 5 ( x 1.0 105 )(1.0 105 ) 1.0 105 x
Kb 1.8 10
[NH 3 ] 0.35 1.0 105 0.35
0.35 1.8 105
Assume x 1.0 105 x = 5
= 0.63 M = initial NH 4 + concentration
1.0 10
0.63 mol NH 4 + 1 mol NH 4 2 SO 4 132.1 g NH 4 2 SO 4
mass NH 4 2 SO 4 = 0.500 L× × ×
1 L soln 2 mol NH 4+ 1 mol NH 4 2 SO 4
Mass of (NH4)2SO4 = 21 g
440
Chapter 17: Additional Aspects of Acid–Base Equilibria
6A (a) For formic acid, pKa log (18. 104 ) 3.74. The Henderson-Hasselbalch equation
provides the pH of the original buffer solution:
[CHO 2 ] 0.350
pH = pKa log 3.74 log 354
.
[ HCHO 2 ] 0.550
(b) The added acid can be considered completely reacted with the formate ion to produce
formic acid. Each mole/L of added acid consumes 1 M of formate ion and forms 1 M of
formic acid: CHO2 (aq) + H3 O (aq) HCHO2 (aq) + H 2 O(l). Kneut = Kb/Kw ≈
+
441
Chapter 17: Additional Aspects of Acid–Base Equilibria
[CHO 2 ] 0.345
pH = pK a + log = 3.74 + log = 3.53
[HCHO2 ] 0.555
(c) Added base reacts completely with formic acid producing, an equivalent amount of
formate ion. This continues until all of the formic acid is consumed.
Each 1 mole of added base consumes 1 mol of formic acid and forms 1 mol of
formate ion: HCHO 2 + OH CHO 2 + H 2O . Kneut = Ka/Kw ≈ 1.8 × 1010. Thus,
CHO 2 = 0.350 M + 0.0050 M = 0.355 M
HCHO2 = 0.550 0.0050 M = 0.545 M . With the Henderson-Hasselbalch equation
CHO 2 0.355
we find pH = pK a + log = 3.74 + log = 3.55
HCHO 0.545
2
6B The buffer cited has the same concentration as weak acid and its anion, as does the buffer of
Example 17-6. Our goal is to reach pH = 5.03 or H 3O + = 10 pH = 105.03 = 9.3 106 M .
c h
Adding strong acid H 3O + , of course, produces HC 2 H 3O 2 at the expense of C2 H 3O 2 .
Thus, adding H+ drives the reaction to the left. Again, we use the data around the balanced
chemical equation.
Equation: HC2 H 3O 2 aq + H 2 O(l)
C 2 H 3O 2 aq + H 3O + aq b g b g
Initial: 0.250 M 0.560 M 8.0 106 M
Add acid: +y M
Form HAc: +y M y M y M
b0.250 + yg M b0.560 yg M 0 M
Changes: x M x M x M
Equil: b 0.250 + y x M g b g
0.560 y + x M 9.3 106 M
6
[H 3 O ][C 2 H 3 O 2 ] 9.3 10 (0.560 y x)
+
5 9.3 106 (0.560 y )
Ka 1.8 10
[HC 2 H 3 O 2 ] 0.250 y x 0.250 y
(Assume that x is negligible compared to y )
b
1.8 105 0.250 + y
6
g
= 0.484 +1.94 y = 0.560 y y=
0.560 0.484
= 0.026 M
9.3 10 1.94 +1.00
Notice that our assumption is valid: x 0.250 + y = 0.276 0.560 y = 0.534 .
0.026 mmol H 3O + 1 mL HNO3 aq
VHNO3 300.0 mL buffer = 1.3 mL of 6.0 M HNO3
1 mL buffer 6.0 mmol H3O +
Instead of the algebraic solution, we could have used the Henderson-Hasselbalch
equation, since the final pH falls within one pH unit of the pKa of acetic acid. We let z
indicate the increase in HC 2 H 3O 2 , and also the decrease in C 2 H 3O 2
C 2 H 3O 2 0.560 z 0.560 z
pH = pKa + log L O = 4.74 + log 0.250 + z = 5.03 = 105.03 4.74 = 1.95
NM HC 2 H 3O 2 QP 0.250 + z
442
Chapter 17: Additional Aspects of Acid–Base Equilibria
0.560 0.488
b g
0.560 z = 1.95 0.250 + z = 0.488 +1.95 z z=
1.95 +1.00
= 0.024 M
This is, and should be, almost exactly the same as the value of y we obtained by the
I.C.E. table method. The slight difference is due to imprecision arising from rounding
errors.
7A (a) The initial pH is the pH of 0.150 M HCl, which we obtain from H 3O + of that
strong acid solution.
0150
. mol HCl 1 mol H 3O +
[H 3O + ] 0150
. M,
1 L soln 1 mol HCl
pH = log [H 3O + ] log (0150
. ) 0.824
(b) To determine H 3O + and then pH at the 50.0% point, we need the volume of the
solution and the amount of H 3O + left unreacted. First we calculate the amount of
hydronium ion present and then the volume of base solution needed for its
complete neutralization.
0.150 mmol HCl 1 mmol H 3O +
amount H 3O = 25.00 mL
+
= 3.75 mmol H 3O +
1 mL soln 1 mmol HCl
1 mmol OH 1 mmol NaOH 1 mL titrant
Vacid = 3.75 mmol H 3O + +
1 mmol H 3O 1 mmol OH 0.250 mmol NaOH
15.0 mL titrant
At the 50.0% point, half of the H3O+ (1.88 mmol H 3O + ) will remain unreacted and
only half (7.50 mL titrant) of the titrant solution will be added. From this information,
and the original 25.00-mL volume of the solution, we calculate H 3O + and then pH.
443
Chapter 17: Additional Aspects of Acid–Base Equilibria
7B b g
(a) The initial pH is simply the pH of 0.00812 M Ba OH 2 , which we obtain from
OH for the solution.
OH =
0.00812 mol Ba OH b g 2
2 mol OH
= 0.01624 M
1 L soln b g
1 mol Ba OH 2
pOH = log OH = log 0.0162 = 1.790; pH = 14.00 pOH = 14.00 1.790 = 12.21
(b) To determine OH and then pH at the 50.0% point, we need the volume of the
solution and the amount of OH unreacted. First we calculate the amount of
hydroxide ion present and then the volume of acid solution needed for its complete
neutralization.
0.00812 mmol Ba OH 2 2 mmol OH
amount OH = 50.00 mL = 0.812 mmol OH
1mL soln 1mmol Ba OH 2
1mmol H 3 O + 1mmol HCl 1mL titrant
Vacid = 0.812 mmol OH
+
= 32.48 mL titrant
1mmol OH 1mmol H 3 O 0.0250 mmol HCl
At the 50.0 % point, half (0.406 mmol OH ) will remain unreacted and only half
(16.24 mL titrant) of the titrant solution will be added. From this information, and
the original 50.00-mL volume of the solution, we calculate OH and then pH.
0.406 mmol OH left
OH = = 0.00613 M
50.00 mL original +16.24 mL titrant
pOH = log 0.00613 = 2.213; pH = 14.00 pOH = 11.79
(c) Since this is the titration of a strong base by a strong acid, at the equivalence
point,pH = 7.00. The solution at this point is neutral because the dominant ionic
species in solution, namely Ba2+(aq) and Cl-(aq), do not react with water to a
detectable extent.
444
Chapter 17: Additional Aspects of Acid–Base Equilibria
8A (a) c
Initial pH is just that of 0.150 M HF ( pKa = log 6.6 104 = 3.18 ).h
0.150 mmol HF
[Initial solution contains 20.00 mL =3.00 mmol HF]
1 mL
Equation : HF aq + H 2O(l) H 3O aq
+
+ F aq
Initial : 0.150 M 0M 0M
Changes : x M +x M +x M
Equil: (0.150 x) M xM xM
H 3 O + F- xx x2
Ka = = = 6.6 104
HF 0.150 x 0.150
x 0.150 6.6 104 9.9 103 M
x 0.05 0.150 . The assumption is invalid. After a second cycle of
approximation, H 3O + = 9.6 103 M ; pH = log 9.6 103 = 2.02
(b) When the titration is 25.0% complete, there are (0.25×3.00=) 0.75 mmol F for
every 3.00 mmol HF that were present initially. Therefore, (3.00-0.75=) 2.25
mmol HF remain untitrated. We designate the solution volume (the volume
holding these 3.00 mmol total) as V and use the Henderson-Hasselbalch equation
to find the pH.
F 0.75 mmol / V
pH = pKa + log = 3.18 + log = 2.70
HF 2.25 mmol / V
(c) At the midpoint of the titration of a weak base, pH = pKa = 3.18.
(d) At the endpoint of the titration, the pH of the solution is determined by the
conjugate base hydrolysis reaction. We calculate the amount of anion and the
volume of solution in order to calculate its initial concentration.
0.150 mmol HF 1 mmol F
amount F = 20.00 mL = 3.00 mmol F
1 mL soln 1 mmol HF
1mmol OH 1 mL titrant
volume titrant = 3.00 mmol HF = 12.0 mL titrant
1mmol HF 0.250 mmol OH
3.00 mmol F
F = = 0.0938 M
20.00 mL original volume +12.0 mL titrant
We organize the solution of the hydrolysis problem around its balanced equation.
Equation : F aq
+ H 2O(l) HF aq + OH aq
Initial: 0.0938M 0M 0M
Changes : xM +x M +x M
Equil : 0.0938 x M xM xM
445
Chapter 17: Additional Aspects of Acid–Base Equilibria
Initial: 0.106 M 0M 0 M
Changes: x M +x M +x M
Equil: b
0.106 x M g xM x M
NH 4 + OH xx x2
Kb = = = 1.8 105
NH
3
0.106 x 0.106
-
x 0.106 1.8 10 4 1.4 103 M = [OH ]
The assumption is valid (x << 0.106).
pOH = log 0.0014 = 2.85 pH = 14.00 – pOH = 14.00 – 2.85 = 11.15
+
(b) When the titration is 25.0% complete, there are 25.0 mmol NH 4 for every 100.0
mmol of NH 3 that were present initially (i.e., there are 1.33 mmol of NH4+ in
solution), 3.98 mmol NH 3 remain untitrated. We designate the solution volume
(the volume holding these 5.30 mmol total) as V and use the basic version of the
Henderson-Hasselbalch equation to find the pH.
1.33 mmol
NH 4 +
pOH = pK b + log = 4.74 + log V = 4.26
NH 3
3.98 mmol
V
pH = 14.00 4.26 = 9.74
(c) At the midpoint of the titration of a weak base, pOH = pK b = 4.74 and pH = 9.26
(d) At the endpoint of the titration, the pH is determined by the conjugate acid
hydrolysis reaction. We calculate the amount of that cation and the volume of the
solution in order to determine its initial concentration.
+
0.106 mmol NH 3 1 mmol NH 4
amount NH 4 +
= 50.00 mL
1 mL soln 1 mmol NH 3
+
amount NH 4 + = 5.30 mmol NH 4
1 mmol H 3O + 1 mL titrant
Vtitrant = 5.30 mmol NH 3 = 23.6 mL titrant
1 mmol NH 3 0.225 mmol H 3O +
446
Chapter 17: Additional Aspects of Acid–Base Equilibria
+
5.30 mmol NH 4
NH 4 + =
50.00 mL original volume + 23.6 mL titrant = 0.0720 M
We organize the solution of the hydrolysis problem around its balanced chemical
equation.
Equation: NH 4 aq + H 2 O(l) NH 3 aq + H 3O aq
+
+
Initial: 0.0720 M 0M 0 M
Changes: x M +x M +x M
Equil: b
0.0720 x M g xM x M
c h
pH = log 6.3 106 = 5.20
9A The acidity of the solution is principally the result of the hydrolysis of the carbonate ion,
which is considered first.
Equation: CO3
2
aq HCO3 aq + OH aq
+ H 2 O(l)
Initial: 1.0 M 0M 0 M
Changes: x M +x M +x M
Equil: b
1.0 x M g x M x M
447
Chapter 17: Additional Aspects of Acid–Base Equilibria
The assumption is valid (y << 0.015) and y = H 2 CO 3 = 2.3 108 M. Clearly, the
second hydrolysis makes a negligible contribution to the acidity of the solution. For the
entire solution, then
pOH = log OH = log 0.015 = 1.82b g pH = 14.00 1.82 = 12.18
9B The acidity of the solution is principally the result of hydrolysis of the sulfite ion.
SO3 aq + H 2 O(l) HSO3 aq + OH aq
2
Equation:
Initial: 0.500 M 0M 0 M
Changes: x M +x M +x M
Equil: b0.500 x M g xM x M
13
H 2SO3 OH y 0.00028 + y 0.00028 y
K b = 7.7 10 = = =y
HSO3 0.00028 y 0.00028
The assumption is valid (y << 0.00028) and y = H 2 SO3 = 7.7 1013 M. Clearly, the
second hydrolysis makes a negligible contribution to the acidity of the solution. For the
entire solution, then
b
pOH = log OH = log 0.00028 = 3.55 g pH = 14.00 3.55 = 10.45
448
Chapter 17: Additional Aspects of Acid–Base Equilibria
INTEGRATIVE EXAMPLE
A. From the given information, the following can be calculated:
pH of the solution = 2.716 therefore, [H+] = 1.92×10-3
FP = 0 C + Tf
Tf = -i K f m
Tf -1 1.86 C / m molality
To determine the number of moles of solute, convert 7.50 g of unknown acid to moles by
using its molar mass. The molar mass can be calculated as follows:
HA H+ + A-
7.50 g
Initial MM 0 0
0.500 L
Change –x x x
7.50 g
MM
Equilibrium 1.92 103 1.92×10-3 1.92×10-3
0.500 L
[H + ][A - ]
2.50 10-5 =
[HA]
(1.92 103 ) 2
2.50 10-5
7.50
MM 1.92 103
0.500
MM =100.4 g/mol
449
Chapter 17: Additional Aspects of Acid–Base Equilibria
1 mol
# moles of solute = 7.50 g 0.0747 mol
100.4 g
Tf = -i K f m
Tf -1 1.86 C / m 0.152 m
Tf -0.283 C
B. By looking at the titration curve provided, one can deduce that the titrant was a strong acid.
The pH before titrant was added was basic, which means that the substance that was titrated was
a base. The pH at the end of the titration after excess titrant was added was acidic, which means
that the titrant was an acid.
~50 mL of 0.2 M strong acid (1×10-2 mol) was needed to reach the equivalence point. This
means that the unknown contained 1×10-2 mol of weak base. The molar mass of the unknown
can be determined as follows:
0.800 g
80 g/mol
1102 mol
EXERCISES
The Common-Ion Effect
1. (a) Note that HI is a strong acid and thus the initial H 3O + = HI = 0.0892 M
Equation :
HC3 H 5 O 2 + H 2 O
C3 H 5 O 2 + H 3 O
+
450
Chapter 17: Additional Aspects of Acid–Base Equilibria
C3 H 5 O 2 H 3 O + x 0.0892 + x 0.0892 x
Ka =
= 1.3 10 5
= x 4.0 105 M
HC3 H 5 O 2 0.275 x 0.275
Kw 1.0 1014
(b) OH = = = 1.1 1013 M
H 3O + 0.0892
c h
Hasselbalch equation, is pH = pKa = log 7.2 104 = 3.14 . Thus, the addition has
caused a pH change of 1.05 units.
(b) NaNO 3 contributes nitrate ion, NO 3 , to the solution. Since, however, there is no
b g
molecular HNO 3 aq in equilibrium with hydrogen and nitrate ions, there is no
equilibrium to be shifted by the addition of nitrate ions. The [H3O+] and the pH are thus
unaffected by the addition of NaNO 3 to a solution of nitric acid. The pH changes are not
the same because there is an equilibrium system to be shifted in the first solution, whereas
there is no equilibrium, just a change in total ionic strength, for the second solution.
451
Chapter 17: Additional Aspects of Acid–Base Equilibria
5. (a) The strong acid HCl suppresses the ionization of the weak acid HOCl to such an
extent that a negligible concentration of H 3O + is contributed to the solution by
HOCl. Thus, H 3O + = HCl = 0.035 M
NO 2
pH = pK a + log = 3.14 + log 0.100 M = 3.40
HNO 2 0.0550 M
Buffer Solutions
Ka =
H 3O + CHO 2
= 1.8 10 4
=
cS + 8.7 10 h8.7 10
5 5
8.7 105 S
; S = 0.76 M
LM HCHO 2 OP 0.366 0.366
N Q
452
Chapter 17: Additional Aspects of Acid–Base Equilibria
CHO 2 CHO 2
4.06 = 3.74 + log ; = 2.1;
HCHO
HCHO CHO 2 = 2.1 0.366 = 0.77 M
2 2
Kb =
NH 4
+
OH
= 1.8 105 =
b
x 0.153 + x
g
0.153x
x = 4.8 105 M
LM NH 3 OP 0.408 x 0.408
N Q
To determine the value of x , we assumed x 0.153 , which clearly is a valid
assumption.
OH = 4.8 105 M; pOH = log 4.8 105 = 4.32; pH = 14.00 4.32 = 9.68
11. (a) 0.100 M NaCl is not a buffer solution. Neither ion reacts with water to a
detectable extent.
(b) 0.100 M NaCl—0.100 M NH 4 Cl is not a buffer solution. Although a weak acid,
NH 4+ , is present, its conjugate base, NH3, is not.
(c) 0.100 M CH 3 NH 2 and 0.150 M CH 3 NH 3+ Cl is a buffer solution. Both the weak
base, CH 3 NH 2 , and its conjugate acid, CH 3NH 3+ , are present in approximately
equal concentrations.
453
Chapter 17: Additional Aspects of Acid–Base Equilibria
(d) 0.100 M HCl—0.050 M NaNO 2 is not a buffer solution. All the NO 2 has
converted to HNO 2 and thus the solution is a mixture of a strong acid and a weak
acid.
(e) 0.100 M HCl—0.200 M NaC 2 H 3O 2 is a buffer solution. All of the HCl reacts
with half of the C 2 H 3O 2 to form a solution with 0.100 M HC 2 H 3O 2 , a weak acid,
and 0.100 M C 2 H 3O 2 , its conjugate base.
(f) 0.100 M HC2 H 3O 2 and 0.125 M NaC3 H 5O 2 is not a buffer in the strict sense
because it does not contain a weak acid and its conjugate base, but rather the
conjugate base of another weak acid. These two weak acids (acetic,
Ka = 1.8 105 , and propionic, Ka = 1.35 105 ) have approximately the same
strength, however, this solution would resist changes in its pH on the addition of
strong acid or strong base, consequently, it could be argued that this system
should also be called a buffer.
Kb =
C 6 H 5 NH 3
+
OH
= 7.4 10 10
=
c2.79 10 6
h
+x x
LMC6 H 5 NH 2 OP 0.105 x
N Q
7.4 1010 0.105 x = 2.79 106 + x x; 7.8 1011 7.4 1010 x = 2.79 106 x + x 2
x 2 + 2.79 106 + 7.4 1010 x 7.8 1011 = 0; x 2 + 2.79 106 x 7.8 1011 0
454
Chapter 17: Additional Aspects of Acid–Base Equilibria
15. (a) First use the Henderson-Hasselbalch equation. pK b = log 1.8 105 = 4.74,
pK a = 14.00 4.74 = 9.26 to determine NH 4 + in the buffer solution.
NH NH NH
pH = 9.45 = pK a + log 3
= 9.26 + log 3
; log 3
= 9.45 9.26 = +0.19
NH 4 +
NH 4 NH 4 +
+
We now assume that the volume of the solution does not change significantly when
the solid is added.
1 L soln 0.17 mol NH 4 1 mol NH 4 2 SO 4
+
mass NH 4 2 SO 4 = 425 mL +
1000 mL 1 L soln 2 mol NH 4
132.1 g NH 4 2 SO 4
= 4.8 g NH 4 2 SO 4
1 mol NH 4 2 SO 4
pH = 9.30 = pK a + log
NH 3
= 9.26 + log
NH 3
log
NH 3
= 9.30 9.26 = +0.04
NH 4
+
NH 4
+
NH 4 +
NH3 = 100.04 = 1.1 =
0.258
0.19 1.1x 0.258 x 0.062 M
+
NH 4
0.17 M + x M
455
Chapter 17: Additional Aspects of Acid–Base Equilibria
17. The added HCl will react with the ammonia, and the pH of the buffer solution will
decrease. The original buffer solution has NH 3 = 0.258 M and NH 4 = 0.17 M .
We first calculate the [HCl] in solution, reduced from 12 M because of dilution. [HCl]
0.55 mL
added = 12 M = 0.066 M We then determine pKa for ammonium ion:
100.6 mL
c h
pKb = log 1.8 105 = 4.74 pKa = 14.00 4.74 = 9.26
NH 3 aq + H 3O + aq NH 4 aq + H 2 O l
+
Equation:
Buffer: 0.258 M ≈0M 0.17 M
Added: +0.066 M
Changes: 0.066 M 0.066 M +0.066 M
Final: 0.192 M 0M 0.24 M
NH 3 0.192
pH = pKa + log L +O
= 9.26 + log = 9.16
NM NH 4 QP 0.24
19. The pKa ’s of the acids help us choose the one to be used in the buffer. It is the acid with a
pKa within 1.00 pH unit of 3.50 that will do the trick. pKa = 3.74 for
HCHO 2 , pKa = 4.74 for HC 2 H 3O 2 , and pK a1 = 2.15 for H 3 PO 4 . Thus, we choose
HCHO 2 and NaCHO 2 to prepare a buffer with pH = 3.50 . The Henderson-Hasselbalch
equation is used to determine the relative amount of each component present in the buffer
solution.
CHO 2 CHO 2
pH = 3.50 = 3.74 + log log = 3.50 3.74 = 0.24
HCHO2
HCHO 2
CHO 2
= 100.24 = 0.58
HCHO 2
This ratio of concentrations is also the ratio of the number of moles of each component
in the buffer solution, since both concentrations are a number of moles in a certain
volume, and the volumes are the same (the two solutes are in the same solution). This
ratio also is the ratio of the volumes of the two solutions, since both solutions being
mixed contain the same concentration of solute. If we assume 100. mL of acid solution,
Vacid = 100. mL . Then the volume of salt solution is
Vsalt = 0.58 100. mL = 58 mL 0.100 M NaCHO 2
456
Chapter 17: Additional Aspects of Acid–Base Equilibria
21. (a) The pH of the buffer is determined via the Henderson-Hasselbalch equation.
C 3 H 5O 2 0.100M
pH = pKa + log L O = 4.89 + log 0.100M = 4.89
NM HC 3 H 5O 2 QP
The effective pH range is the same for every propionate buffer: from pH = 3.89
to pH = 5.89 , one pH unit on either side of pKa for propionic acid, which is 4.89.
(b) To each liter of 0.100 M HC3 H 5O 2 — 0.100M NaC 3 H 5O 2 we can add 0.100
mol OH before all of the HC3 H 5O 2 is consumed, and we can add 0.100 mol
H 3O + before all of the C 3 H 5O 2 is consumed. The buffer capacity thus is 100.
millimoles (0.100 mol) of acid or base per liter of buffer solution.
23. (a) The pH of this buffer solution is determined with the Henderson-Hasselbalch equation.
CHO 2
= log 1.8 104 + log 8.5 mmol/75.0 mL
pH = pK a + log
15.5 mmol/75.0 mL
HCHO 2
2 mmol OH
(b) Amount of added OH = 0.25 mmol Ba OH 2 b g 1 mmol Ba OHb g = 0.50 mmol OH
2
The OH added reacts with the formic acid and produces formate ion.
Equation: HCHO 2 (aq) + OH (aq)
CHO 2 (aq) + H 2 O(l)
Buffer: 15.5 mmol 0M 8.5 mmol
Add base: +0.50 mmol
React: 0.50 mmol 0.50 mmol +0.50 mmol
Final: 15.0 mmol 0 mmol 9.0 mmol
CHO 2
= log 1.8 104 + log 9.0 mmol/75.0 mL
pH = pK a + log
15.0 mmol/75.0 mL
HCHO 2
457
Chapter 17: Additional Aspects of Acid–Base Equilibria
25. (a) We use the Henderson-Hasselbalch equation to determine the pH of the solution.
The total solution volume is
36.00 mL + 64.00 mL = 100.00 mL. pK a = 14.00 pK b = 14.00 + log 1.8 105 = 9.26
[NH 3 ] 0.0720 M
pH = pK a log
9.26 log 9.01 9.00
[NH 4 ] 0.128 M
(c) The 0.20 mL of added 1.00 M HCl does not significantly affect the volume of the
solution, but it does add 0.20 mL 1.00 M HCl = 0.20 mmol H 3O + . This added
458
Chapter 17: Additional Aspects of Acid–Base Equilibria
Acid–Base Indicators
27. (a) The pH color change range is 1.00 pH unit on either side of pKHln . If the pH color
change range is below pH = 7.00 , the indicator changes color in acidic solution. If
it is above pH = 7.00 , the indicator changes color in alkaline solution. If pH = 7.00
falls within the pH color change range, the indicator changes color near the neutral
point.
Indicator K HIn pK HIn pH Color Change Range Changes Color in?
Bromphenol blue 1.4 104 3.85 2.9 (yellow) to 4.9 (blue) acidic solution
Bromcresol green 2.1 105 4.68 3.7 (yellow) to 5.7 (blue) acidic solution
Bromthymol blue 7.9 108 7.10 6.1 (yellow) to 8.1 (blue) neutral solution
2,4-Dinitrophenol 1.3 104 3.89 2.9 (colorless) to 4.9 (yellow) acidic solution
Chlorophenol red 1.0 106 6.00 5.0 (yellow) to 7.0 (red) acidic solution
Thymolphthalein 1.0 1010 10.00 9.0 (colorless) to 11.0 (blue) basic solution
(b) If bromcresol green is green, the pH is between 3.7 and 5.7, probably about pH = 4.7 .
If chlorophenol red is orange, the pH is between 5.0 and 7.0, probably about pH = 6.0 .
459
Chapter 17: Additional Aspects of Acid–Base Equilibria
29. (a) In an Acid–Base titration, the pH of the solution changes sharply at a definite pH
that is known prior to titration. (This pH change occurs during the addition of a
very small volume of titrant.) Determining the pH of a solution, on the other hand,
is more difficult because the pH of the solution is not known precisely in
advance. Since each indicator only serves to fix the pH over a quite small region,
often less than 2.0 pH units, several indicators—carefully chosen to span the
entire range of 14 pH units—must be employed to narrow the pH to 1 pH unit
or possibly lower.
(b) An indicator is, after all, a weak acid. Its addition to a solution will affect the
acidity of that solution. Thus, one adds only enough indicator to show a color
change and not enough to affect solution acidity.
31. (a) 0.10 M KOH is an alkaline solution and phenol red will display its basic color in
such a solution; the solution will be red.
(b) 0.10 M HC 2 H 3O 2 is an acidic solution, although that of a weak acid, and phenol
red will display its acidic color in such a solution; the solution will be yellow.
(c) 0.10 M NH 4 NO 3 is an acidic solution due to the hydrolysis of the ammonium ion.
Phenol red will display its acidic color, that is, yellow, in this solution.
(d) 0.10 M HBr is an acidic solution, the aqueous solution of a strong acid. Phenol red
will display its acidic color in this solution; the solution will be yellow.
(e) 0.10 M NaCN is an alkaline solution because of the hydrolysis of the cyanide ion.
Phenol red will display its basic color, red, in this solution.
(f) An equimolar acetic acid–potassium acetate buffer has pH = pKa = 4.74 for acetic
acid. In this solution phenol red will display its acid color, namely, yellow.
460
Chapter 17: Additional Aspects of Acid–Base Equilibria
titration rises very sharply ( 6 pH units for an addition of only 2 drops (0.10
mL)).
Neutralization Reactions
0.43mmol OH
OH = = 4.3 103 M
100.0 mL soln
pOH = log 4.3 103 = 2.37 pH = 14.00 2.37 = 11.63
Titration Curves
39. First we calculate the amount of HCl. The relevant titration reaction is
HCl aq + KOH aq KCl aq + H 2 O(l)
461
Chapter 17: Additional Aspects of Acid–Base Equilibria
FG
4.00 mmol H 3O 2.42 mmol OH
1 mmol H 3O + IJ
[H 3O + ] =
H 1 mmol OH K
= 0.0451 M
25.00 mL originally +10.00 mL titrant
b g
pH = log 0.0451 = 1.346
0.242 mmol OH
(b) amount OH = 15.00 mL = 3.63 mmol OH ; H3O+ is in excess.
1 mL soln
FG
4.00 mmol H 3O 3.63 mmol OH
1 mmol H 3O + IJ
[H 3O + ] =
H 1 mmol OH K
= 0.00925 M
25.00 mL originally +15.00 mL titrant
b g
pH = log 0.00925 = 2.034
c h
pKa = log 7.2 104 = 3.14
NO 2
1.16 mmol NO 2 / 35.00 mL
pH = pKa + log L O = 3.14 + log = 2.87
MN HNO 2 QP 2.14 mmol HNO 2 / 35.00 mL
462
Chapter 17: Additional Aspects of Acid–Base Equilibria
43. In each case, the volume of acid and its molarity are the same. Thus, the amount of acid is
the same in each case. The volume of titrant needed to reach the equivalence point will
also be the same in both cases, since the titrant has the same concentration in each case,
and it is the same amount of base that reacts with a given amount (in moles) of acid.
Realize that, as the titration of a weak acid proceeds, the weak acid will ionize,
replenishing the H 3O + in solution. This will occur until all of the weak acid has ionized
and all of the released H+ has subsequently reacted with the strong base. At the
equivalence point in the titration of a strong acid with a strong base, the solution contains
ions that do not hydrolyze. But the equivalence point solution of the titration of a weak
acid with a strong base contains the anion of a weak acid, which will hydrolyze to
produce a basic (alkaline) solution. (Don’t forget, however, that the inert cation of a
strong base is also present.)
463
Chapter 17: Additional Aspects of Acid–Base Equilibria
Since the pH changes very rapidly at the equivalence point, from about pH = 10
to about pH = 4 , most of the indicators in Figure 17-8 can be used. The main
exceptions are alizarin yellow R, bromphenol blue, thymol blue (in its acid range),
and methyl violet.
(b) Initial pH:
Since this is the titration of a weak base with a strong acid, NH4Cl is the solute
present at the equivalence point, and since NH4+ is a slightly acidic cation, the pH
should be slightly lower than 7. The titration reaction is:
NH 4 + OH x2 x2
Kb = = 1.8 105 =
NH 3 1.00 x 1.00
464
Chapter 17: Additional Aspects of Acid–Base Equilibria
Equation : NH 4 + aq + H 2 O(l)
NH 3 aq + H 3 O + aq
Initial : 0.200 M 0M 0M
Changes : x M + xM + xM
Equil : 0.200 x M xM xM
K w 1.0 1014 NH 3 H 3O
+
x2 x2
Ka = = = =
Kb 1.8 105
NH 3 0.200 x 0.200
(x << 0.200, thus the approximation is valid)
x = 1.1105 M; H 3O + = 1.1105 M; pH = log 1.1105 = 4.96
Of the indicators in Figure 17-8, one that has the pH of the equivalence point
within its pH color change range is methyl red (yellow at pH = 6.2 and red at
pH = 4.5); Bromcresol green would be another choice. At the 50% titration point,
NH 3 = NH 4 + and pOH = pK b = 4.74 pH = 14.00 4.74 = 9.26
47. A pH greater than 7.00 in the titration of a strong base with a strong acid means that the
base is not completely titrated. A pH less than 7.00 means that excess acid has been
added.
(a) We can determine OH of the solution from the pH. OH is also the quotient
of the amount of hydroxide ion in excess divided by the volume of the solution:
20.00 mL base + x mL added acid.
pOH = 14.00 pH = 14.00 12.55 = 1.45 OH = 10 pOH = 101.45 = 0.035 M
3.50 0.200 x = 0.70 + 0.035 x; 3.50 0.70 = 0.035 x + 0.200 x; 2.80 = 0.235 x
465
Chapter 17: Additional Aspects of Acid–Base Equilibria
2.80
x= = 11.9 mL acid added.
0.235
(b) The set-up here is the same as for part (a).
pOH = 14.00 pH = 14.00 10.80 = 3.20 OH = 10 pOH = 103.20 = 0.00063 M
0.175 mmol OH 0.200 mmol H 3O +
20.00 mL base
x mL acid
1mL base 1mL acid
[OH ]
20.00 mL + x mL
mmol
[OH ] 0.00063 = 0.00063M
mL
3.50 0.200 x = 0.0126 + 0.00063 x; 3.50 0.0126 = 0.00063 x + 0.200 x; 3.49 = 0.201 x
3.49
x= = 17.4 mL acid added. This is close to the equivalence point at 17.5 mL.
0.201
(c) Here the acid is in excess, so we reverse the set-up of part (a). We are just slightly
beyond the equivalence point. This is close to the “mirror image” of part (b).
H3O + = 10 pH = 104.25 = 0.000056 M
[H O ] =
3
+ H 1 mL acid K H 1mL base K
20.00 mL+ x mL
= 5.6 105 M
0.200 x 3.50 = 0.0011+ 5.6 105 x; 3.50 + 0.0011 = 5.6 105 x + 0.200 x;
3.50 = 0.200 x
3.50
x= = 17.5 mL acid added, which is the equivalence point for this titration.
0.200
49. For each of the titrations, the pH at the half-equivalence point equals the pKa of the acid.
x2
The initial pH is that of 0.1000 M weak acid: K a x [H 3 O ]
0.1000 x
x must be found using the quadratic formula roots equation unless the approximation is
valid.
One method of determining if the approximation will be valid is to consider the ratio Ca/Ka. If
the value of Ca/Ka is greater than 1000, the assumption should be valid, however, if the value of
Ca/Ka is less than 1000, the quadratic should be solved exactly (i.e., the 5% rule will not be
satisfied).
466
Chapter 17: Additional Aspects of Acid–Base Equilibria
The pH at the equivalence point is that of 0.05000 M anion of the weak acid, for which
the OH is determined as follows.
Kw x2 Kw
Kb = x= 0.05000 [OH ]
K a 0.05000 Ka
We can determine the pH at the quarter and three quarter of the equivalence point by
using the Henderson-Hasselbalch equation (effectively + 0.48 pH unit added to the
pKa).
And finally, when 0.100 mL of base has been added beyond the equivalence point, the
pH is determined by the excess added base, as follows (for all three titrations).
0.1000 mmol NaOH 1 mmol OH
0100
. mL
1mL NaOH soln 1 mmol NaOH
OH = = 4.98 104 M
20.1 mL soln total
c h
pOH = log 4.98 104 = 3.303 pH = 14.000 3.303 = 10.697
(a) Ca/Ka = 14.3; thus, the approximation is not valid and the full quadratic equation
must be solved.
Initial: From the roots equation x = [H 3 O ] 0.023M pH=1.63
Half equivalence point: pH = pKa = 2.15
pH at quarter equivalence point = 2.15 - 0.48 = 1.67
pH at three quarter equivalence point = 2.15 + 0.48 = 2.63
1.0 1014 pOH 6.57
Equiv: x = OH = 0.05000 2.7 107
7.0 10 3
pH 14.00 6.57 7.43
Indicator: bromthymol blue, yellow at pH = 6.2 and blue at pH = 7.8
(b) Ca/Ka = 333; thus, the approximation is not valid and the full quadratic equation
must be solved.
Initial: From the roots equation x = [H 3 O ] 0.0053M pH=2.28
Half equivalence point: pH = pKa = 3.52
pH at quarter equivalence point = 3.52 - 0.48 = 3.04
pH at three quarter equivalence point = 3.52 + 0.48 = 4.00
1.0 1014
Equiv: x = OH = 4
0.05000 1.3 106
3.0 10
pOH 5.89
pH = 14.00 5.89 811
.
Indicator: thymol blue, yellow at pH = 8.0 and blue at pH = 9.6
Initial: [ H 3O ] 01000
. 2.0 108 0.000045 M pH = 4.35
467
Chapter 17: Additional Aspects of Acid–Base Equilibria
. 1014
10
Equiv: x = OH = 8
. 104
0.0500 16
2.0 10
pOH 380
.
pH 14.00 380
. 10.20
Indicator: alizarin yellow R, yellow at pH = 10.0 and violet at pH = 12.0
The three titration curves are drawn with respect to the same axes in the diagram below.
12
10
8
pH
0
0 2 4 6 8 10 12
Volume of 0.10 M NaOH added (mL)
468
Chapter 17: Additional Aspects of Acid–Base Equilibria
The graphs look to be mirror images of one another. In reality, one must reflect about a
horizontal line centered at pH or pOH = 7 to obtain the other curve.
0.100 M NaOH(25.00 mL) + 0.100 M HCl 0.100 M NaOH(25.00 mL) + 0.100 M HCl
14 14
12 12
10 10
8
pOH
pH
6 6
4
4
2
2
0
0
0 10 20 30 40 50 60
Volume of HCl (mL) 0 10 20 30 40 50 60
Volume of HCl (mL)
H 3 PO 4 aq + CO3 aq
H 2 PO 4 aq + HCO3 aq
2
55. (a)
H 2 PO 4 aq + CO3 aq
HPO 4 2 aq + HCO3 aq
2
HPO 4
2
aq + OH aq
PO 43 aq + H 2O(l)
K a 2 {H 3 PO 4 } 6.3 108
2
H 2 PO 4 + CO3 2
HPO 4 + HCO3 K 1.3 103
K a 2 {H 2 CO3 } 4.7 1011
K a 3 {H 3 PO 4 } 4.2 10 13
2 2
HPO 4 + CO 3 3
PO 4 + HCO3
K 11
8.9 10 3
K a 2 {H 2 CO3 } 4.7 10
Since the equilibrium constant for the third reaction is much smaller than 1.00, we
conclude that it proceeds to the right to only a negligible extent and thus is not a
3
practical method of producing PO 4 . The other two reactions have large
469
Chapter 17: Additional Aspects of Acid–Base Equilibria
59. (a) b g
Ba OH 2
is a strong base.
pOH = 14.00 11.88 = 2.12 OH = 10 2.12 = 0.0076 M
b g
Ba OH =
0.0076 mol OH 1 mol Ba OH 2
b g = 0.0038 M
2
1L 2 mol OH
470
Chapter 17: Additional Aspects of Acid–Base Equilibria
C2 H 3O 2 0.294 M
(b) pH = 4.52 = pK a + log
= 4.74 + log
HC 2 H 3O 2 HC 2 H 3O 2
0.294 M 0.294 M
log = 4.52 4.74 = 100.22 = 0.60
HC 2 H 3O 2
HC 2 H 3O 2
0.294 M
HC2 H3O2 = = 0.49 M
0.60
61. (a) A solution can be prepared with equal concentrations of weak acid and conjugate
base (it would be a buffer, with a buffer ratio of 1.00, where the pH = pKa = 9.26).
Clearly, this solution can be prepared, however, it would not have a pH of 6.07.
(b) These solutes can be added to the same solution, but the final solution will have an
b g
appreciable HC 2 H 3O 2 because of the reaction of H 3O + aq with C 2 H 3O 2 aq b g
Equation: H 3O + (aq) + C2 H3O 2 (aq) HC 2 H 3O 2 (aq) + H 2 O(l)
Initial 0.058 M 0.10 M 0M
Changes: –0.058 M –0.058 M +0.058 M
Equil: ≈0.000 M 0.04 M 0.058 M
+
Of course, some H 3O will exist in the final solution, but not equivalent to 0.058 M HI.
(c) Both 0.10 M KNO 2 and 0.25 M KNO 3 can exist together. Some hydrolysis of the
b g
b g
NO 2 aq ion will occur, forming HNO 2 aq and OH-(aq).
(d) BabOH g is a strong base and will react as much as possible with the weak
2
(e) This will be a benzoic acid–benzoate ion buffer solution. Since the two
components have the same concentration, the buffer solution will have
c h
pH = pKa = log 6.3 105 = 4.20 . This solution can indeed exist.
(f) The first three components contain no ions that will hydrolyze. But C2 H3O 2 is
the anion of a weak acid and will hydrolyze to form a slightly basic solution.
Since pH = 6.4 is an acidic solution, the solution described cannot exist.
471
Chapter 17: Additional Aspects of Acid–Base Equilibria
(a) Since we add V mL of HCl solution (and each mL adds 1.00 mmol H3O+ to the
solution), we have added V mmol H3O+ to the solution. Now the final [H3O+] = 10–1.00
= 0.100 M.
472
Chapter 17: Additional Aspects of Acid–Base Equilibria
V mmol H 3 O
[H 3 O ] 0.100 M
(250.0 V ) mL
25.0
V 25.0 0.100 V , therefore, V 27.8 mL added
0.900
Now, we check our assumptions. The total solution volume is 250.0 mL+ 27.8 mL =
277.8 mL There are 25.0 mmol HC2H3O2 present before equilibrium is established,
and 27.8 mmol H3O+ also.
25.0 mmol 27.8 mmol
[HC 2 H 3 O 2 ] 0.0900 M [H 3 O ] 0.100 M
277.8 mL 277.8 mL
Equation:
HC3H 5O 2 (aq) H 2 O(l)
C3H 5O 2 (aq) H 3O (aq)
Initial: 0.0900 M 0 M 0.100 M
Changes: -x M xM x M
Equil: (0.08999 x)M xM (0.100 x)M
We have assumed that all of the C3H5O2– is obtained from the NaC3H5O2 solution,
since the addition of that ion in the solution should suppress the ionization of
HC3H5O2.
(c) We let V be the final volume of the solution.
Initial: 25.0/V 0M 0M
Changes: x/V M x/V M x/V M
Equil: (25.0/V x/V) M x/V M x/V M
473
Chapter 17: Additional Aspects of Acid–Base Equilibria
[ H 3 O ] [C 3 H 5 O 2 ] (x /V )2 x2 /V
Ka 1.35 10 5
[HC 3 H 5 O 2 ] 25.0 / V x / V 25.0
0.29 mmol
When V = 250.0 mL, x = 0.29 mmol H3O+ [H 3 O ] 1.2 10 3 M
250.0 mL
pH = –log(1.2 × 10–3) = 2.92
An increase of 0.15 pH unit gives pH = 2.92 + 0.15 = 3.07
[H3O+] = 10–3.07 = 8.5 × 10–4 M This is the value of x/V. Now solve for V.
1.2 × 10–3 M), we would obtain V = 4.8 × 102 mL. The answer to the problem thus
is sensitive to the last significant figure that is retained. We obtain V = 4.6 × 102
mL, requiring the addition of 2.1 × 102 mL of H2O.
Another possibility is to recognize that [H3O+] K a Ca for a weak acid with
ionization constant Ka and initial concentration Ca if the approximation is valid.
If Ca is changed to Ca/2, [H3O+] K a C a 2 2. Since, pH = –log [H3O+], the
change in pH given by:
pH log 2 log 21 / 2 0.5 log 2 0.5 0.30103 0.15 .
This corresponds to doubling the solution volume, that is, to adding 250 mL water.
Diluted by half with water, [H3O+] goes down and pH rises, then (pH1 – pH2) < 0.
66. (a) At a pH = 2.00, in Figure 17-9 the pH is changing gradually with added NaOH. There
would be no sudden change in color with the addition of a small volume of NaOH.
(b) At pH = 2.0 in Figure 17-9, approximately 20.5 mL have been added. Since,
equivalence required the addition of 25.0 mL, there are 4.5 mL left to add.
Therefore,
4.5
% HCl unneutralized 100% 18%
25.0
69. (a) We concentrate on the ratio of concentrations of which the logarithm is taken.
[conjugate base]eq equil. amount conj. base f initial amt. weak acid f
[weak acid]eq equil. amount weak acid (1 f ) initial amt. weak acid 1 f
The first transformation is the result of realizing that the volume in which the weak acid
and its conjugate base are dissolved is the same volume, and therefore the ratio of
equilibrium amounts is the same as the ratio of concentrations. The second
474
Chapter 17: Additional Aspects of Acid–Base Equilibria
transformation is the result of realizing, for instance, that if 0.40 of the weak acid has
been titrated, 0.40 of the original amount of weak acid now is in the form of its
conjugate base, and 0.60 of that amount remains as weak acid. Equation 17.2 then is:
pH = pKa + log (f /(1 – f ))
0.27
(b) We use the equation just derived. pH 10.00 log 9.56
1 0.23
475
Chapter 17: Additional Aspects of Acid–Base Equilibria
73. (a) Equation (1) is the reverse of the equation for the autoionization of water.
Thus, its equilibrium constant is simply the inverse of Kw.
1 1
K 14
1.00 1014
K w 1.0 10
Equation (2) is the reverse of the hydrolysis reaction for NH4+. Thus, its equilibrium
constant is simply the inverse of the acid ionization constant for NH4+, Ka =
5.6 × 10-10
1 1
K' 1.8 10 9
K a 5.6 10 10
(b) The extremely large size of each equilibrium constant indicates that each reaction goes
essentially to completion. In fact, a general rule of thumb suggests that a reaction is considered
essentially complete if Keq > 1000 for the reaction.
77. For both titration curves, we assume 10.00 mL of solution is being titrated and the
concentration of the solute is 1.00 M, the same as the concentration of the titrant. Thus,
10.00 mL of titrant is required in each case. (You may be able to sketch titration curves
based on fewer calculated points. Your titration curve will look slightly different if you
make different initial assumptions.)
(a) The initial pH is that of a solution of HCO3–(aq). This is an anion that can ionize to
CO32 (aq) or be hydrolyzed to H2CO3(aq). Thus,
pH 12 (pK a1 pK a2 ) 12 (6.35 10.33) 8.34
The final pH is that of 0.500 M H2CO3(aq). All of the NaOH(aq) has been
neutralized, as well as all of the HCO3–(aq), by the added HCl(aq).
Equation:
H 2 CO3 (aq) H 2 O(l) HCO3 (aq) H3 O (aq)
Initial: 0.500 M 0M 0M
Changes: xM xM xM
Equil: (0.500 x ) M xM xM
[HCO3 ][H 3 O ] xx x2
Kb 4.43 107
[H 2 CO3 ] 0.500 x 0.500
(Ca /K a = 1.1×106 ; thus, the approximation is valid)
[OH ] 0.500 4.4 107 4.7 104 M pH 3.33
During the course of the titration, the pH is determined by the Henderson-
Hasselbalch equation, with the numerator being the percent of bicarbonate ion
remaining, and as the denominator being the percent of bicarbonate ion that has been
transformed to H2CO3.
10% 90%
90% titrated: pH = 6.35 + log 5.40 10% titrated: pH = 6.35 + log 7.30
90% 10%
476
Chapter 17: Additional Aspects of Acid–Base Equilibria
5% 95%
95% titrated: pH = 6.35 + log 5.07 5% titrated: pH = 6.35 + log 7.63
95% 5%
After the equivalence point, the pH is determined by the excess H3O+.
0.50 mL 1.00 M
At 105% titrated, [H 3 O ] 0.024 pH 1.61
20.5 mL
2.00 mL 1.00 M
At 120% titrated, [H 3 O ] 0.091 M pH 1.04
22.0 mL
The titration curve derived from these data is sketched below.
9
8
7
6
5
pH
4
3
2
1
0
0 2 4 6 8 10 12
Volume 1.00 M HCl
(b) The final pH of the first step of the titration is that of a solution of HCO3–(aq). This
is an anion that can be ionized to CO32–(aq) or hydrolyzed to H2CO3(aq). Thus,
pH 12 (pK a1 pK a 2 ) 12 (6.35 10.33) 8.34 . The initial pH is that of 1.000 M
CO32–(aq), which pH is the result of the hydrolysis of the anion.
Equation: CO32 (aq)
H 2 O(l) HCO3 (aq) OH (aq)
Initial: 1.000 M 0M 0M
Changes: x M x M x M
Equil: (1.000 x) M xM xM
[HCO3 ][OH ] K w 1.0 1014 4 xx x2
Kb 2.1 10
[CO32 ] K a2 4.7 1011 1.000 x 1.000
477
Chapter 17: Additional Aspects of Acid–Base Equilibria
10% 90%
90% titrated: pH 10.33 log 9.38 10% titrated: pH 10.33 log 11.28
90% 10%
5% 95%
95% titrated: pH 10.33 log 9.05 5% titrated: pH 10.33 log 11.61
95% 5%
During the course of the second step of the titration, the values of pH are precisely as
they are for the titration of NaHCO3, except the titrant volume is 10.00 mL more (the
volume needed to reach the first equivalence point). The solution at the second
equivalence point is 0.333 M H2CO3, for which the set-up is similar to that for 0.500 M
H2CO3.
[H 3 O ] 0.333 4.4 10 7 3.8 10 4 M pH 3.42
After the equivalence point, the pH is determined by the excess H3O+.
0.50 mL 1.00 M
At 105% titrated, [H3O ] 0.0164 M pH 1.8
30.5 mL
2.00 mL 1.00 M
At 120% titrated, [H3O ] 0.0625 M pH 1.20
32.0 mL
12
10
8
pH
0
-3 2 7 12 17 22
Volume 1.00 M HCl, mL
478
Chapter 17: Additional Aspects of Acid–Base Equilibria
endpoint occurs at about pH = 3.3 and is the result of the second equivalence point
of Na2CO3. The mass of Na2CO3 can be determined as follows:
1L 0.1000 mol HCl 1 mol HCO3 1 mol Na 2 CO3
mass Na 2 CO3 0.78 mL
1000 mL 1 L soln 1 mol HCl 1 mol HCO3
105.99 g Na 2 CO3
0.0083 g Na 2 CO3
1 mol Na 2 CO3
0.0083g
% Na 2 CO3 100 8.3% Na 2 CO3 by mass
0.1000g
81. (a) A buffer solution is able to react with small amounts of added acid or base. When strong acid is
added, it reacts with formate ion.
CHO 2 (aq) H 3 O (aq)
HCHO 2 (aq) H 2 O
HC 2 H 3 O 2 (aq) OH (aq)
H 2 O(l) C 2 H 3 O 2 (aq)
Therefore neither added strong acid nor added strong base alters the pH of the solution very much.
Mixtures of this type are referred to as buffer solutions.
(b) We begin with the two ionization reactions.
HCHO 2 (aq) H 2 O(l) CHO 2 (aq) H 3 O (aq)
C2 H 3 O 2 (aq) H 3 O (aq)
HC2 H 3 O 2 (aq) H 2 O(l)
479
Chapter 17: Additional Aspects of Acid–Base Equilibria
0.150 K A
0.150 K A y K A xy y
KA x
0.250 K F
0.250 K F z K F xz z
KF x
Then we substitute these expressions into equation (1) and solve for x.
0.150 K A 0.250 K F
0.250 x 0.250 since x 0.250
KA x KF x
0.250 ( K F x) ( K A x) 0.150 K A ( K F x) 0.250 K F ( K A x)
K A K F ( K A K F ) x x 2 1.60 K A K F x(0.600 K A 1.00 K F )
x 2 0.400 K A x 0.600 K A K F 0 x 2 7.2 10 6 x 1.9 10 9
7.2 10 6 5.2 10 11 7.6 10 9
x 4.0 10 5 M [H 3 O ]
2
pH 4.40
(c) Adding 1.00 L of 0.100 M HCl to 1.00 L of buffer of course dilutes the
concentrations of all components by a factor of 2. Thus, [Na+] = 0.125 M; total
acetate concentration = 0.0750 M; total formate concentration = 0.125 M. Also, a
new ion is added to the solution, namely, [Cl–] = 0.0500 M.
[ Na ] 0.125 [OH ] 0 [H 3 O ] x [Cl ] 0.0500 M [C 2 H 3 O 2 ] y [CHO 2 ] z
0.0750 [HC 2 H 3 O 2 ] [C 2 H 3 O 2 ] [HC 2 H 3 O 2 ] 0.0750 – [C 2 H 3 O 2 ] 0.0750 y
0.125 [HCHO 2 ] [CHO 2 ] [HCHO 2 ] 0.125 [CHO 2 ] 0.125 z
[ Na ] [H 3 O ] [C 2 H 3 O 2 ] [OH ] [CHO 2 ] [Cl ] (electroneutrality)
0.125 x [C 2 H 3 O 2 ] [CHO 2 ] [Cl ] y z 0 0.0500 0.075 x y z
[H 3 O ][C 2 H 3 O 2 ] x y
K A 1.8 10 5
[ HC 2 H 3 O 2 ] 0.0750 y
[H 3 O ][CHO 2 ] xz
K F 1.8 10 4
[HCHO 2 ] 0.125 z
480
Chapter 17: Additional Aspects of Acid–Base Equilibria
Then we substitute these expressions into equation (1) and solve for x.
0.0750 K A 0.125 K F
0.0750 x 0.0750 since x 0.0750
KA x KF x
0.0750 (K F x) (K A x) 0.0750 K A (K F x) 0.125 K F (K A x)
K A K F (K A K F )x x 2 2.67 K A K F x(1.67 K F 1.00 K A )
x 2 0.67 K F x 1.67 K A K F 0 x 2 1.2 10 4 x 5.4 10 9
(a) Bromthymol blue or phenol red would be good indicators for this titration since they change
color over this pH range.
481
Chapter 17: Additional Aspects of Acid–Base Equilibria
(b) The H2PO4–/HPO42- system would be suitable because the pKa for the acid (namely, H2PO4–) is
close to the equivalence point pH of 7.93. An acetate buffer would be too acidic, an ammonia
buffer too basic.
482
Chapter 17: Additional Aspects of Acid–Base Equilibria
84. Let's consider some of the important processes occurring in the solution.
H 2 PO 4 (aq) OH (aq)
(1) HPO 4 2 (aq) H 2 O(l) K (1) = K a2 4.2 10-13
2
H 3 O (aq) PO 43 (aq) 1.0 1014
(2) HPO 4 (aq) H 2 O(l) K (2) = K b 8
1.6 107
6.3 10
H 3 O (aq) NH 3 (aq) 1.0 1014
(3) NH 4 (aq) H 2 O(l) K (3) = K a 5.6 1010
1.8 105
H 2 O(l) NH 3 (aq) 1
(4) NH 4 (aq) OH - (aq) K (4) 5.6 104
1.8 105
May have interaction between NH 4 and OH - formed from the hydrolysis of HPO 4 2 .
H 2 PO 4 - (aq) NH 3 (aq)
NH 4 (aq) HPO 4 2 (aq)
Initial 0.10M 0.10M 0 M 0 M
Change x x x x
Equil. 0.100 x 0.100 x x x
(where x is the molar concentration of NH 4 that hydrolyzes)
[H 2 PO 4 - ] [NH 3 ] [x]2
K 2
2
9.0 103 and x 8.7 103 M
[NH 4 ] [HPO 4 ] [0.10-x]
89. (a) We start by writing the equilibrium expression for all reactions:
CO 2 aq K 2 Ca 2 CO32
K1
CO 2 g
HCO3 CO 2 aq
K3 K4
H 3O CO32 HCO3 H 3O
483
Chapter 17: Additional Aspects of Acid–Base Equilibria
HCO3
H 3O
K 3 CO32
CO aq
H 3O 2
K 4 HCO3
From the expression for K1, we know that [CO2(aq)] = K1[CO2(g)]. Therefore,
K CO g
H 3O 1 2 2
2
K 3 K 4 CO3
Now, the expression for K2 can be plugged into the above expression as follows:
K CO g K1 CO 2 g Ca 2
H 3O 1 2 2
2
K 3 K 4 CO3 K2 K3 K 4
K1 CO 2 g Ca 2
H 3O
K 2 K3 K 4
2.684 108 M
484
Chapter 17: Additional Aspects of Acid–Base Equilibria
91. (a) We note that the pH is 5.0. Therefore, H 3O 105.0 1.0 105 M
C K a H 3O 2.0 102 1.8 105 1.0 105
4.6 103
1.8 10 1.0 10
2 5 5 2
K a H 3O
(b)
dCA d pH d pH dCA
d pH 1.0 103 4.6 103 0.22
pH 5 0.22 4.78
(c) At an acetic acid concentration of 0.1 M, C is also 0.1, because C is the total concentration of
the acetic acid and acetate. The maximum buffer index β (2.50×10-2) happens at a pH of 4.75,
where [HAc] = [Ac–]. The minima are located at pH values of 8.87 (which correspond to pH of a
solution of 0.1 M acetic acid and 0.1 M acetate, respectively).
3.0E-02
2.5E-02
2.0E-02
1.5E-02
β
1.0E-02
5.0E-03
0.0E+00
0 1 2 3 4 5 6 7 8 9
pH
FEATURE PROBLEMS
92. (a) The two curves cross the point at which half of the total acetate is present as
acetic acid and half is present as acetate ion. This is the half equivalence point in a
titration, where pH = pKa = 4.74 .
(b) For carbonic acid, there are three carbonate containing species: “ H 2 CO 3 ” which
predominates at low pH, HCO3 , and CO 2 3 , which predominates in alkaline
485
Chapter 17: Additional Aspects of Acid–Base Equilibria
c h
pH = pKa 2 = log 4.7 1011 = 10.33 . The following graph was computer-
calculated (and then drawn) from these equations. f in each instance represents
the fraction of the species whose formula is in parentheses.
1 K1 K1 K 2
= 1+ +
f H2A H + 2
H +
1 H + K2
= +1+
f HA K1 H +
2
1 H + H +
= + +1
f A 2 K1 K 2 K2
f H 2 CO3
f HCO3
f CO3 2
(c) For phosphoric acid, there are four phosphate containing species: H 3 PO 4 under acidic
2 3
conditions, H 2 PO 4 , HPO 4 , and PO 4 , which predominates in alkaline solution. The points
of intersection should occur at pH = pKa1 = log 7.1 103 = 2.15, c h
pH = pKa2 = log 6.3 10 c 8
h = 7.20 , and pH = pK a3 = logc4.2 10 h = 12.38 , a quite alkaline
13
486
Chapter 17: Additional Aspects of Acid–Base Equilibria
PO34 PO
f Hf 3(H 4) -
f (H PO )
f H 2 PO24 4
f (HPO42-)
f HPO4 2 3-
f (PO4 )
f PO43
SELF-ASSESSMENT EXERCISES
98. (a) HCHO2 + OH¯ → CHO2¯ + H2O
CHO2¯ + H3O+ → HCHO2 + H2O
487
Chapter 17: Additional Aspects of Acid–Base Equilibria
14
13
12
11
10
9
8
pH
7
6
5
4
3
2
1
0
(b) The pH at the equivalence point is ~5.3 for a 0.1 M solution. Use methyl red.
14
13
12
11
10
9
8
pH
7
6
5
4
3
2
1
0
(c) The pH at the equivalence point is ~8.7 for a 0.1 M solution. Use phenolphthalein, because it
just begins to get from clear to pink around the equivalence point.
488
Chapter 17: Additional Aspects of Acid–Base Equilibria
14
13
12
11
10
9
8
pH
7
6
5
4
3
2
1
0
(d) The pH for the first equivalence point (NaH2PO4– to Na2HPO42–) for a 0.1 M solution is right
around ~7, so use bromthymol blue.
14
13
12
11
10
9
8
pH
7
6
5
4
3
2
1
0
100. (a) This is the initial equilibrium before any base has reacted with the acid. The reaction that
dominates, along with changes in concentration, is shown below:
489
Chapter 17: Additional Aspects of Acid–Base Equilibria
H 3O + C7 H 5O-2
Ka
HC7 H5O2
6.3 10-5
x x
0.0100 - x
Solving for x using the quadratic formula, x = 7.63 104 M.
pH = log H3O+ log 7.63 104 3.12
(b) In this case, we titrate the base with 0.00625 L of Ba(OH)2. Therefore, we have to calculate the
final moles of the base and the total volume to determine the concentration.
mol HC7 H 5O 2 0.02500 L 0.0100 M HC7 H 5O 2 2.5 104 mol
2 mol OH
mol OH 0.00625 L 0.0100 M Ba OH 2
= 1.25 104 mol
1 mol Ba OH 2
Since the amount of OH¯ is half of the initial amount of HC7H5O2, the moles of HC7H5O2 and
C7H5O2¯ are equal. Therefore, Ka = [H3O+], and pH = −log(6.3×10-5) = 4.20.
(c) At the equivalence point, there is initially no HC7H5O2. The equilibrium is dominated by
C7H5O2¯ hydrolyzing water. The concentration of C7H5O2¯ is:
Total moles of HC7H5O2 = 2.5×10-4 mol as shown previously. At the equivalence point, the
moles of acid equal moles of OH¯.
1 mol Ba OH 2
mol Ba OH 2 2.5 104 mol OH
1.25 104 mol
2 mol OH
Vol of Ba(OH)2 = 1.25×10-4 mol / 0.0100 M = 0.0125 L
Total volume of the solution at the equivalence point is the sum of the initial volume plus the
volume of Ba(OH)2 added. That is,
Since this is a base reaction, K b K w K a 1.00 104 6.3 105 1.587 1010.
490
Chapter 17: Additional Aspects of Acid–Base Equilibria
OH - HC7 H 5O 2
Kb =
C7 H 5O-2
1.59 1010
x x
0.00667 x
solving for x (by simplifying the formula above) yields x = 1.03 106 M.
pH = 14 pOH 14 log 1.03 106 14 6.00 8.00
(d) In this part, we have an excess of a strong base. As such, we have to determine how much
excess base there is and what is the final volume of the solution.
mol Ba OH 2 2 mol OH
mol OH 0.01500 L 0.0100
L 1 mol Ba OH 2
3.000 104 mol OH
101. The answer is (c); because of the common ion-effect, the presence of HCO2¯ will repress ionization
of formic acid.
102. The answer is (d), because NaHCO3 is a weak base and will react with protons in water, shifting the
formic acid ionization equilibrium to the right.
103. The answer is (b), raise the pH. NH4+ is an acid, and to be converted to its conjugate base, it must
react with a base to abstract its proton.
104. The answer is (b), because at that point, the number of moles of weak base remaining is the same as
its conjugate acid, and the equilibrium expression simplifies to Ka = [H3O+].
105. The base, C2H5NH2, is reacted with HClO4. The reaction is:
C2 H 5 NH 2 HClO 4 C2 H 5 NH 3 ClO 4
491
Chapter 17: Additional Aspects of Acid–Base Equilibria
1.001 mol
C2 H 5 NH 3 0.5005 M
2L
C2 H 5 NH 3 OH 0.5005 +x x
4
4.3 10
C2 H5 NH 2 0.2445 x
x 2.10 104
pOH log 2.10 104 3.68
pH 14 3.68 10.32
106. We assume that all of Ca(HSe)2 dissociates in water. The concentration of HSe– is therefore:
2 mol HSe
0.5 M Ca HSe 2 1.0 M HSe
1 mol Ca HSe 2
–
We note that HSe is amphoteric; that is, it can act either as an acid or a base. The acid reaction of
HSe– and the concentration of [H3O+] generated, are as follows:
1.00 10 11
Se 2 H 3O
x x
HSe
1.00 x
x = 1.00 1011 3.16 106
The basic reaction of HSe– and the concentration of [OH–] generated, are as follows:
Kb = 1.00×10-14/1.3×10-4 = 7.69×10-11
11
H 2Se OH x x
7.69 10
HSe
1.00 x
x = 7.69 1011 8.77 106
Therefore, we have [H3O+] = 3.16×10-6 and [OH–] = 8.77×10-6. Since these two react to give H2O,
the result is 8.77×10-6 – 3.16×10-6 = 5.61×10-6 M [OH–]. The pH of the solution is:
107. The answer is (a). The solution system described is a buffer, and will resist large changes in pH.
Adding KOH should raise the pH slightly.
492
Chapter 17: Additional Aspects of Acid–Base Equilibria
108. The answer is (b), because HSO3¯ is a much stronger acid (Ka = 1.3×10-2) than H2PO4¯
(Ka = 6.3×10-8).
109. The answer is (b). The pKa of the acid is 9, which puts it squarely in the middle of the 8–10 pH
range for the equivalence point.
110. (a) NaHCO3 titrated with NaOH: pH > 7, because HCO3¯ is itself slightly basic, and is being
titrated with NaOH to yield CO32- at the equivalence point, which is even more basic.
(b) HCl titrated with NH3: pH < 7, because the resulting NH4+ at the equivalence point is acidic.
(c) KOH titrated with HI: pH = 7, because a strong base is being titrated by a strong acid, and the
resulting anions and cations are all non-basic and non-acidic.
493