Beruflich Dokumente
Kultur Dokumente
AQUEOUS EQUILIBRIA
11.1
(a) When solid sodium acetate is added to an acetic acid solution, the
concentration of H 3 O + decreases because the equilibrium
HC 2 H 3 O 2 (aq) + H 2 O(l) U H 3 O + (aq) + C 2 H 3 O 2 (aq)
11.3
[H3 O+ ][A ]
[A ]
If [A ] = [HA], then
; pK a = pH log
(a) K a =
[HA]
[HA]
pK a = pH.
pH = pK a = 3.08, K a = 8.3 104
SM-314
Concentration
(mol L1 )
HL(aq)
H 2 O(l)
H 3 O + (aq)
L (aq)
initial
2x
change
+y
+y
2x y
y+x
equilibrium
Ka =
[H 3 O + ][L ] ( y ) (y + x) ( y ) (x)
=
= 8.3 104
[HL]
(2x y )
(2x)
11.5
[SO4 2 ]
[base]
K
=
+
pH = pK a + log
p
log
[acid]
[HSO4 ]
0.25 mol L1
= 1.62, pOH = 14.00 1.62 = 12.38
(a) pH = 1.92 + log
1
0.5 mol L
0.10 mol L1
= 1.22, pOH = 12.78
(b) pH = 1.92 + log
1
0.50 mol L
(c) pH = pK a = 1.92, pOH = 12.08
See solution to Exercise 11.3.
11.7
= 0.17 mol L
0.050 L 41.99 g NaF
Concentration
(mol L1 )
initial
HF(aq)
0.40
H 2 O(l)
SM-315
H 3 O + (aq)
F (aq)
0.17
+x
+x
0.40 x
0.17 + x
change
equilibrium
Ka =
= 3.5 104
[HF]
(0.40 x)
(0.40)
11.9
Concentration
(mol L1 ) HCN(aq)
H 2 O(l)
H 3 O + (aq)
CN (aq)
initial
1.5 102
__
2.1 102
change
__
+x
+x
__
2.1 102 + x
= 4.9 1010
2
2
[HCN]
(1.5 10 x)
(1.5 10 )
x 3.5 1010 mol L1 [H 3 O + ]
pH = log[H 3 O + ] = log(3.5 1010 ) = 9.46
(b) The solution here is the same as for part (a), except for the initial
concentrations:
SM-316
K a = 4.9 1010 =
x = [H 3 O + ] = 2.0 10 10 mol L1
K a = 4.9 1010 =
(x)[NaCN]0
= x = [H3 O + ]
[HCN]0
pH = pK a = log(4.9 10 10 ) = 9.31
[ClO ]
Hasselbalch equation: pH = pK a + log
, or
[HClO]
[ClO ]
log
= pH pK a = 6.50 7.53 = 1.03
[HClO]
[ClO ]
= 9.3 102
[HClO]
11.13 The rule of thumb we use is that the effective range of a buffer is roughly
within plus or minus one pH unit of the pK a of the acid. Therefore,
(a) pK a = 3.08; pH range, 24
(b) pK a = 4.19; pH range, 35
SM-317
11.15 Choose a buffer system in which the conjugate acid has a pK a close to the
desired pH. Therefore,
(a) HClO 2 and NaClO2 , pK a = 2.00
(b) NaH 2 PO4 and Na 2 HPO4 , pK a2 = 7.21
(c) CH 2 ClCOOH and NaCH 2 ClCO 2 , pK a = 2.85
(d) Na 2 HPO 4 and Na 3 PO 4 , pK a = 12.68
11.17 (a) HCO 3 (aq) + H 2 O(l) L CO 32 (aq) + H 3 O + (aq)
K a2 =
[H 3 O + ][CO3 2 ]
, pK a2 = 10.25
[HCO3 ]
[CO3 2 ]
pH = pK a2 + log
[HCO3 ]
[CO3 2 ]
= pH pK a2 = 11.0 10.25 = 0.75
log
[HCO3 ]
[CO3 2 ]
= 5.6
[HCO3 ]
(b) [CO3 2 ] = 5.6 [HCO3 ] = 5.6 0.100 mol L1 = 0.56 mol L1
moles of CO 3 2 = moles of K 2 CO 3 = 0.56 mol L1 1 L = 0.56 mol
138.21 g K 2 CO3
mass of K 2 CO3 = 0.56 mol
= 77 g K 2 CO3
1 mol K 2 CO3
[CO3 2 ] 0.100 mol L1
=
= 1.8 102 mol L1
(c) [HCO3 ] =
5.6
5.6
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[CH3 CO2 ]
11.19 (a) pH = pK a + log
(see Exercise 11.23)
[CH 3 COOH]
0.100
pH = pK a + log
= 4.75 (initial pH)
0.100
final pH: (0.0100 L) (0.950 mol L1 ) = 9.50 103 mol NaOH (strong
base) produces 9.50 103 mol CH 3 CO 2 from CH 3 COOH
[CH3 COOH] =
[CH3 CO 2 ] =
SM-319
11.21
14
(b)
pH at stoichiometric
point = 7.0
(a) initial pH = 1
0
10
20
1L
1 mL
1 mol HCl
1 L HCl
1
[Na + ] = (0.0250 L)
1L
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0.150 mol
(d) number of moles of H 3 O + (from acid) = (0.0200 L)
1L
3
+
= 3.00 10 mol H 3 O
0.110 mol Na +
number of moles of OH (from base) = (0.0250 L)
1L
= 2.75 10 mol OH
excess H 3 O + = (3.00 2.75) 10 3 mol = 2.5 104 mol H 3 O +
[H 3 O + ] =
present:
1 L HCl
1.14 g
100% = 71.7%
1.592 g
0.110 mol
(b) initial moles of OH (from base) = (0.0250 L)
1L
= 2.75 10 mol OH
SM-321
0.150 mol
4
+
moles of H 3 O + added = (0.0050 L)
= 7.5 10 mol H 3 O
1
L
3
excess OH = (2.75 0.75) 10 mol = 2.00 10 3 mol OH
2.00 103 mol
= 0.067 mol L1
0.030 L
pOH = log(0.067) = 1.17, pH = 14.00 1.17 = 12.83
[OH ] =
(d) pH = 7.00
1 mol HCl
1 L HCl
VHCl = (2.75 103 mol NaOH)
1
(e) [H 3 O + ] = (0.0050 L)
1L
= 0.028 mol L
1L
0.0533 L
pH = log(0.028) = 1.55
initial
0.10
change
+x
+x
equilibrium
0.10 x
Ka =
[H 3 O + ][CH 3 CO 2 ]
x2
x2
= 1.8 105 =
[CH 3 COOH]
0.10 x 0.10
SM-322
x 2 = 1.8 106
x = 1.3 103 mol L1 = [H 3 O + ]
initial pH = log(1.3 103 ) = 2.89
[H3 O+ ][CH 3 CO 2 ]
[CH 3 COOH]
Concentration
(mol L1 )
initial
4.29 102
2.86 102
change
+x
+x
2.86 102 + x
( x) ( x + 2.86 102 )
; assume + x and x negligible.
(4.29 102 x)
SM-323
Concentration
0.050
change
+x
+x
0.050 x
equilibrium
K w 1.00 1014
x2
x2
10
Kb =
=
= 5.6 10 =
Ka
0.050 x 0.050
1.8 105
x 2 = 2.8 1011
x = 5.3 106 mol L1 = [OH ]
pOH = 5.28, pH = 14.00 5.28 = 8.72
[NH 4 + ][OH ]
11.33 (a) K b =
= 1.8 105
[NH 3 ]
Concentration
(mol L1 )
H 2 O(l)
NH3 (aq)
NH 4 + (aq)
OH (aq)
initial
0.15
change
+x
+x
equilibrium
0.15 x
1.8 10
x2
x2
=
0.15 x 0.15
SM-324
Concentration
(mol L1 )
H 2 O(l)
initial
change
equilibrium
NH3 (aq)
2.7 102
NH 4 + (aq)
OH (aq)
5.0 102
+x
+x
5.0 102 + x
2.7 102 x
[NH 4 + ][OH ]
= 1.8 105
Kb =
[NH 3 ]
(x) (5.0 102 + x)
; assume that + x and x are negligible
=
(2.7 102 x)
[OH ] = x = 9.7 106 mol L1 and pOH = 5.01
Therefore, pH = 14.00 5.01 = 8.99
(c) At the stoichiometric point, moles of NH 3 = moles of HCl
volume HCl added =
K w 1.00 1014
Ka =
=
= 5.6 1010
5
Kb
1.8 10
Concentration
(mol L1 )
NH 4 + (aq)
initial
0.060
change
+x
H 2 O(l)
SM-325
H 3 O + (aq)
NH 3 (aq)
0
+x
equilibrium 0.060 x
K a = 5.6 1010 =
x2
x2
0.060 x 0.060
11.35 At the stoichiometric point, the volume of solution will have doubled;
initial
0.10
change
+x
+x
equilibrium
0.10 x
Kb =
K w 1.00 1014
=
= 5.6 1010
5
Ka
1.8 10
[HCH 3 CO 2 ][OH ]
x2
x2
Kb =
=
= 5.6 1010
0.10 x 0.10
[CH 3 CO 2 ]
x = 7.5 106 mol L1 = [OH ]
pOH = log(7.5 106 ) = 5.12, pH = 14.00 5.12 = 8.88
From Table 11.2, we see that this pH value lies within the range for
phenolphthalein, so that indicator would be suitable; the others would not.
11.37 Exercise 11.31: thymol blue or phenolphthalein; Exercise 11.33: methyl
SM-326
11.41 (a) The base HPO32 is the fully deprotonated form of phosphorous acid
(b) To reach the second stoichiometric point would require double the
amount of solution calculated in (a), or 44.0 mL.
Concentration
(mol L1 )
initial
0.0298
__
change
+x
+x
final
0.0298 x
+x
+x
SM-327
[H 3 O + ][HP ]
Ka =
= 1.0 102
[H 2 P]
1.0 102 =
xx
x2
=
0.0298 x 0.0298 x
(b) First, carry out the reaction between phosphorous acid and the strong
base to completion:
H 2 P(aq) + OH (aq)
HP (aq) + H 2 O(l)
[H 2 P] =
Concentration
(mol L1 )
initial
0.0109
__
0.0155
change
__
+x
+x
final
0.0109 x
__
0.0155 + x
+x
SM-328
(0.0155 + x) x
0.0109 x
x = 1.08 102
pH = 1.96
Concentration
(mol L1 )
HP
initial
2.48 10 2
2.29 10 12
change
final 2.48 10 2 x
H3O+
H2P
2.29 10 12 x
H 2O
__
+x
__
__
100 =
( 2.48 10
x )( 2.29 1012 x )
to completion first:
HPO 4 2 (aq) + H 3 O + (aq)
H 2 PO 4 + H 2 O(l)
Initially, moles of
HPO 4
SM-329
Because this reaction proceeds with no excess base or acid, we are dealing
with a solution that can be viewed as being composed of H 2 PO 4 . The
problem then becomes one of estimating the pH of this solution, which
can be done from the relationship
pH = 12 (pK a1 + pK a 2 )
pH = 12 (2.12 + 7.21) = 4.66
(b) This reaction proceeds as in (a), but there is more strong acid
available, so the excess acid will react with H 2 PO 4 to produce H3 PO 4 .
Addition of the first 50.0 mL of acid solution will convert all the HPO 4 2
into H 2 PO 4 . The additional 25.0 mL of the strong acid will react with
H 2 PO 4 :
H 2 PO 4 (aq) + H 3 O + (aq)
H 3 PO 4 (aq) + H 2 O(l)
0.0069 mol
= 0.055. The appropriate relationship
0.125 L
to use is then
Concentration
(mol L1 ) H 3 PO 4 (aq) + H 2 O(l) U H 2 PO 4 (aq) + H 3 O + (aq)
initial
0.055
__
0.055
change
__
+x
+x
final
0.055 x
__
0.055 + x
+x
K a1 =
[H 2 PO 4 ][H 3 O + ]
[H 3 PO 4 ]
Because the equilibrium constant is not small compared to 0.055, the full
quadratic solution must be calculated:
x 2 + 0.055 x = 7.6 103 (0.055 x)
SM-330
intial
0.092
__
0.092
change
__
+x
+x
final
0.092 x
__
0.092 + x
+x
K a 2 = 6.2 108 =
[HPO 4 2 ][H 3 O + ]
[H 2 PO 4 ]
[0.092 + x][H 3 O + ]
= 6.2 108
[0.092 x]
assuming x << than 0.092
x = [H 3 O + ] = 6.2 108
SM-331
+ Cl (aq)
initial
0.20
change
+S
+S
equilibrium
S + 0.20
SM-332
0.150
change
+S
+ 2S
0.150 + 2S
equilibrium
in 0.225 NaCl
(c) Concentration ( mol L1 ) PbCl2 (s) U Pb 2+ (aq)
2 Cl (aq)
initial
2 0.025 = 0.05
change
+S
+S
equilibrium
S + 0.05
2.5 103
change
+S
+ 2S
__
2.5 103 + S
2S
equilibrium
SM-333
S 2 = 1.6 1012
S = 1.3 106 mol L1 = molar solubility of Fe(OH) 2 in 2.5 103 M FeCl2
11.55 (a) Ag + (aq) + Cl (aq) U AgCl(s)
Concentration (mol L1 )
Ag +
Cl
initial
1.0 105
change
+x
equilibrium
0
1.0 105
Concentration (mol L1 )
initial
change
Ni 2+
OH
0.060
equilibrium
0.060
+x
SM-334
1 mL
3
5
11.59
1 drop = 0.05 mL = 0.05 10 L = 5 10 L
20
drops
= 2 10
0.010 L
0.010 L
Will precipitate, because Qsp (2 107 ) > Ksp (1.6 1010 )
(b) Pb2+ (aq) + 2 Cl (aq) U PbCl2 (s), [Pb 2+ ][Cl ]2 = Ksp
2
= 1 10
0.010 L
0.010 L
Will not precipitate, because Qsp (1 1011 ) < Ksp (1.6 105 )
11.61 (a) K sp [Ni(OH) 2 ] < K sp [Mg(OH) 2 ] < K sp [Ca(OH) 2 ]
This is the order for the solubility products of these hydroxides. Thus, the
order of precipitation is (first to last): Ni(OH) 2 , Mg(OH) 2 , Ca(OH) 2 .
(b) Ksp [Ni(OH)2 ] = 6.5 1018 = [Ni 2+ ][OH ]2
6.5 1018
= 6.5 1015
0.0010
[OH ] = 8.1 108
[OH ]2 =
[OH ] =
5.5 106
= 7.4 102
0.0010
pOH = log(7.4 102 ) = 1.13 pH = 14.00 1.13 = 12.87, pH 13
[OH ] =
6.4 109
BaF2
1.7 106
MgCO3
1.0 105
BaCO3
8.1 109
Change
+x
+2x
+x
+x
Ksp = x 2
Solving this for MgCO3 gives 0.0032 M and for BaCO3 gives
9.0 105 M. Clearly, the solubility difference is greatest between the two
carbonates, and CO 32 is the better choice of anion.
11.65 Cu(IO3 ) 2 ( Ksp = 1.4 107 ) is more soluble than
SM-336
essentially all the Pb(IO3 )2 has precipitated. Thus, we expect very little
Pb 2 + to be the left in solution by the time we reach the point at which
S=
SM-337
2.0 1017
= 2.0 103 mol L1 = [Zn 2+ ]
14
1.0 10
= molar solubility of Zn(OH) 2 at pH = 7.0
S=
2.0 1017
= 2.0 101 = 0.20 mol L1 = [Zn 2+ ]
1.0 1016
= molar solubility of Zn(OH)2 at pH = 6.0
S=
(a) Multiply the second equilibrium equation by 2 and add to the first
equilibrium:
Kb =
[HF][OH ]
[F ]
2.9 1011 =
[HF][1 107 ]
[F ]
SM-338
K b = 2.9 1011
K sp = 4.0 1011
K sp = [Ca 2+ ][F ]2
4.0 1011 = x(2 x) 2 = 4 x3
x = 2.2 104
molar solubility = 2.2 104 mol L1
(c) At
pH = 3.0, [H 3 O + ] = 1 10 3 mol L1 and [OH ] = 1 1011 mol L1 .
[HF][OH ]
[F ]
2.9 1011 =
[HF][1 1011 ]
[F ]
SM-339
K sp = 7.7 1013
K f = 5.6 108
K = 4.3 104
[Ag(CN) 2 ][Br ]
= 4.3 104
Hence, K =
[CN ]2
Concentration
(mol L1 ) AgBr(s) + 2 CN (aq) U Ag(CN) 2 (aq) + Br (aq)
initial
change
equilibrium
0.10
2S
0.10 2 S
+S
+S
[Ag(CN) 2 ][Br ]
S2
=
= 4.3 104
[CN ]2
(0.10 2 S ) 2
S
= 4.3 104 = 2.1 102
0.10 2S
S = (2.1 103 ) (4.2 102 S )
Concentration
(mol L1 ) AgCl(s) + 2 HN 3 (aq) U Ag(NH 3 ) 2 + (aq) + Cl (aq)
initial
1.00
change
2 x
+x
+x
final
1.00 2 x
+x
+x
K=
[Ag(NH 3 ) 2 + ][Cl ]
= 2.6 103
2
[NH 3 ]
[ x][ x]
x2
=
[1.00 2 x]2 [1.00 2 x]2
x
0.051 =
1.00 2 x
2.6 103 =
x = 0.046
0.046 mol AgCl will dissolve in 1.00 L of aqueous solution. The molar
mass of AgCl is
143.32 g mol1 ; this corresponds to 0.046
mol L1 142.32 g mol1 = 6.5 g L1 .
For AgI, the same calculation gives x = 4.9 105 mol L1 . The molar
mass of AgI is 234.77 g mol1 , giving a solubility of
4.9 105 mol L1 234.77 g mol1 = 0.023 g L1 .
Thus, we could treat a 0.10 g sample of the compound with
20.0 mL of 1.00 M NH 3 . The AgCl would all dissolve, whereas
practically none of the AgI would.
Note: AgI is also slightly yellow in color, whereas AgCl is white, so an
initial distinction could be made based upon the color of the sample.
11.75 In order to use qualitative analyses, the sample must first be dissolved.
SM-341
pK a = 10.89
K a = 1.288 1011 =
1.288 1011
= 6.45 1010
0.020
[Base form]
. The K a value for
[Acid form]
acetic acid is 1.8 10 5 and pK a = 4.74. Because we are adding acid, the
pH will fall upon the addition and we want the final pH to be no more than
0.20 pH units different from the initial pH, or 4.54.
4.54 = 4.74 + log
0.20 = log
[Base form]
[Acid form]
[Base form]
[Acid form]
[Base form]
= 0.63
[Acid form]
We want the concentration of the base form to be 0.63 times that of the
acid form. We do not know the initial number of moles of base or acid
SM-342
forms, but we know that the two amounts were equal. Let C = initial
number of moles of acetic acid and the initial number of moles of sodium
acetate. The number of moles of H 3 O + to be added (in the form of
HCl(aq)) is 0.001 00 L 6.00 mol L1 = 0.006 00 mol. The total final
volume will be 0.1010 L.
C 0.006 00
0.1010 L
= 0.63
C + 0.006 00
0.1010 L
C 0.006 00
= 0.63
C + 0.006 00
C 0.006 00 = 0.63(C + 0.006 00)
C 0.006 00 = 0.63 C + 0.003 78
0.37 C = 0.009 78
C = 0.026
The initial buffer solution must contain at least 0.026 mol acetic acid and
0.026 mol sodium acetate. The concentration of the initial solution will
then be 0.026 mol 0.100 L = 0.260 M in both acetic acid and sodium
acetate.
11.81 It stands to reason that if the solution desired has a higher pH than the one
SM-343
0.200 M
= 0.348 M
0.575
[A ]
[A ]
= 4.19 + log
pH = 4.35 = pKa + log
[HA]
[HA]
[A ]
= 104.35 4.19 = 1.45
[HA]
To achieve this ratio, we must increase [A ]. Fixing [HA] at 0.348 M,
the concentration of [A ] needed is: [A ] = 1.45 0.348 M = 0.502 M.
Therefore, [A ] needs to increase by: 5.02 M 0.200 M = 0.302 M.
To determine the number of grams of conjugate base needed:
pH
12.0
6.62
1.24
0
25.0
50.0
Vb (L)
(b) 28.6 mL
(c) 1.24
(d) Because this is a titration of a strong acid with a strong base, the pH at
the equivalence point will be 7.00.
11.85 The strong acid, HCl, will protonate the HCO 2 ion.
SM-344
Concentration
(mol L1 ) HCOOH(aq) + H 2 O(l) U H 3 O + (aq) + HCO 2 (aq)
initial
4.4 103
8.9 102
change
+x
+x
equilibrium
4.4 103 x
8.9 102 + x
K a = 1.8 10
Gr
R T
Ka = e
(8.3145 JK
-1
mol-1 ( 298 K )
= 1.74 105
(b) Given the acidity constant above, the mass of sodium acetate needed
is:
pK a = 10 K a = 4.76
pH = pK a + log
[A ]
[A ]
= 4.8 = 4.76 + log
[HA]
[HA]
SM-345
[A ]
= 104.8 4.76 = 1.10
[HA]
Given [HA] = 1.0 M,
[CH 3 CO 2 ]
0.50
= pK a + log
[CH 3 COOH]
0.150
(a) (0.0100 L)(1.2 mol L1 ) = 1.2 102 mol HCl added (a strong acid)
Produces 1.2 102 mol CH 3 COOH from CH 3 CO 2 after adding HCl:
(0.100 L) (0.150 mol L1 ) 1.2 102 mol
[CH 3 COOH] =
+
0.110 L
0.110 L
= 0.245 mol L1
(0.100 L) (0.50 mol L1 ) 1.2 102 mol
[CH 3 CO 2 ] =
0.110 L
0.110 L
= 0.345 mol L1
SM-346
0.345
pH = 4.75 + log
= 4.75 + 0.15 = 4.90 (after adding HCl)
0.245
(b) (0.0500 L) (0.095 mol L1 ) = 4.7 103 mol NaOH added (a strong
base)
Produces 4.7 103 mol CH 3 CO 2 from CH 3 COOH after adding NaOH:
(0.100 L) (0.150 mol L1 ) 4.7 103 mol
[CH 3 COOH] =
0.1500 L
0.150 L
= 6.9 102 mol L1
(0.100 L) (0.50 mol L1 ) 4.7 103 mol
+
[CH 3 CO 2 ] =
0.150 L
0.150 L
3.6 101
= 4.75 + 0.72 = 5.47 (after adding base)
pH = 4.75 + log
2
6.9 10
11.93 CaF2 (s) U Ca 2 + (aq) + 2 F (aq)
= 1.3 10 = Qsp
0.200 0.200
Because Qsp (1.3 1013 ) is less than Ksp (6.2 1012 ), no precipitate will
form.
SM-347
PbF2(s)
Pb2+(aq) + 2 F(aq)
K = 3.7108
The buffer will provide a source of H3O+(aq) ions which will allow the
reaction:
H3O+(aq) + F
HF(aq) + H2O(l)
K = 1/(Ka(HF)) = 1/(3.5104) =
2.86103
These two coupled reactions give two equilibrium expressions which must
be simultaneously satisfied:
[F ]2 [Pb 2+ ] = 1.7 106
and
[HF]
= 2.86 103
+
[H 3O ][F ]
Given that all fluoride ions come from PbF2(s) and wind up as either
F(aq) or HF(aq), and that for every one mole of Pb2+(aq) generated two
moles of F(aq) are also produced, we can write a third equation which
relates the concentration of the fluoride containing species to the
concentration of dissolved barium:
[Pb2+] = ([F] + [HF]) .
In the end, the concentration of Pb2+(aq) will be equal to the solubility of
PbF2(s). To determine the equilibrium concentration of Pb2+(aq), we first
determine [H3O+], which is fixed by the buffer system, and then use the
three simultaneous equations above to solve for [Pb2+]eq.
The buffer determines the equilibrium concentration of H3O+(aq). The
initial concentration of H3O+(aq) and NaCH3CO2(aq) are:
+
[H 3 O ]i =
= 0.0825 M and
0.10 L
( 0.045 L ) ( 0.65 mol L-1 )
= 0.293 M.
[CH 3 CO 2 ]i =
0.10 L
To determine their equilibrium concentrations we solve using the familiar
method:
SM-348
Concentration
(mol L1 ) CH 3 COOH(aq) + H 2 O(l) U H 3 O + (aq) + CH 3 CO 2 (aq)
initial
0.0825
change
+x
equilibrium
K a = 1.8 105 =
0.0825 x
0.293
x
0.292 x
1
2
[HF]
= 2.86 103.
+
[H 3O ][F ]
Due to the presence of the buffer, [H3 O+ ] = 7.1 106 and this last equation
simplifies to
[HF]
= 2.03 102.
[F ]
Rearranging these three simultaneous equations we find:
[Pb 2+ ] =
3.7 108
, [HF] = [F ] ( 2.03 102 ) ,
[F ]2
[Pb 2+ ] =
1
2
and
([F ] + [HF])
3.7 108 1
= 2 [F ] + [F ] ( 2.03 102 ) . Solving this expression for [F ] :
[F ]2
3.7 108
= 4.14 103.
[F ] =
0.5203
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Then, because the volume of the solution has doubled, [HSO 4 ] = 0.10 M ,
Concentration
(mol L1 )
initial
0.10
change
+x
+x
0.10 x
equilibrium
Ka 2
x2
= 0.012 =
0.10 x
0.0012 0.012 x = x 2
x 2 + 0.012 x 0.0012 = 0
pH = log(0.029) = 1.54
(2) second stoichiometric point:
HSO 4 (aq) + OH (aq)
SO 4 2 (aq) + H 2 O(l) . Because the volume of
SM-350
Concentration
(mol L1 ) SO 4 2 (aq) + H 2 O(l) U HSO 4 (aq)
+ OH (aq)
initial
0.067
1 107
change
+x
+x
1 107 + x
equilibrium 0.067 x
( x) (1 107 + x)
K b = 8.3 10 =
0.067 x
3
7
x = [HSO 4 ] = 1.9 10 mol L1
x=
1.6 1010
= 4.0 109 mol L1
4.0 102
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4.0 109
102 = 4.0 105 %
(d) percentage Ag remaining =
0.010
+
11.105 The K sp value for PbF2 obtained from Table 11.5 is 3.7 108. Using this
CaC2O4(s)
K sp = 10
pK sp
Ca2+(aq) + C2O42(aq)
= 108.59 = 2.57 109
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[CO 2 ]
[H 3 O + ][HCO3 ]
H 3 O + (aq)
initial
1.4410-6
5.510-6
change
+ HCO 3 (l)
U 2 H 2 O(l)
K = 7.9 107 =
+ CO 2 (aq)
3.4510-18
+x
3.4510-18 + x
3.45 1018 + x
(1.44 10
x )( 5.5 106 + x )
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