Fundamentals of Analytical Chemistry: 8th ed.

Chapter 10

Chapter 10

10-1 (a) Activity, aA, is the effective concentration of a chemical species A in solution. The

activity coefficient, γA, is the numerical factor necessary to convert the molar

concentration of the chemical species A to activity as shown below:

aA=γA[A]

(b) The thermodynamic equilibrium constant refers to an ideal system within which each

chemical species is unaffected by any others. A concentration equilibrium constant takes

into account the influence exerted by solute species upon one another. The

thermodynamic equilibrium constant is numerically constant and independent of ionic

strength; the concentration equilibrium constant depends upon molar concentrations of

reactants and products as well as other chemical species that may not participate in the

equilibrium.

10-2

Activity coefficients have the following properties:

1. The activity coefficient depends on the solution ionic strength.

2. In very dilute solutions, the activity coefficient approaches unity.

3. For a given ionic strength, the activity coefficient becomes smaller as the charge of the

chemical species increases.

4. At any ionic strength, the activity coefficients are approximately equal for chemical

species having the same charge state.

→
10-3 (a) MgCl 2 + 2 NaOH ←
Mg(OH ) 2 ( s ) + 2 NaCl

Replacing divalent-Mg2+ with Na+ causes the activity coefficient to increase (i.e.,
Fundamentals of Analytical Chemistry: 8th ed. Chapter 10

approach 1.0). Thus, the ionic strength decreases.

→
(b) HCl + NaOH ←
H 2 O + NaCl

The activity coefficient remains relatively constant when the NaOH (strong base) is

added to HCl (strong acid). There is no change in the charge states of the ions present in

the solution equilibria. The ionic strength is unchanged.

→
(c) HOAc + NaOH ←
H 2 O + NaOAc

The activity coefficient will decrease when the NaOH (strong base) is added to the acetic

acid (weak acid) generating water, Na+ and OAc- (conjugate base). Thus, the ionic

strength increases.

10-4 (a) The ionic strength will increase when FeCl3 is added to HCl.

→
(b) 3NaOH + FeCl 3 ←
Fe(OH ) 3 ( s ) + 3NaCl

Addition of FeCl3 to NaOH replaces a univalent OH- with univalent Cl-; thus, the ionic

strength is unchanged.

→
(c) 3AgNO 3 + FeCl 3 ←
Fe( NO 3 ) 3 + 3AgCl( s )

Addition of FeCl3 replaces the univalent Ag+ with the trivalent Fe3+; thus, the ionic

strength increases.

10-5 The initial slope of the change of activity coefficient for Ca2+ is steeper than that for K+

because activity coefficients for multiply-charged ions deviate from ideality (unity) more

than activity coefficients for singly-charged ions.

10-6 The chemical species NH3 is not charged; therefore, the activity coefficient is unity.
Fundamentals of Analytical Chemistry: 8th ed. Chapter 10

10-7 (a) µ =
1
2
([0.040]( 2) 2 + [0.040]( 2) 2 ) = 0.16

(b) µ =
1
2
([0.40](1) 2 + [0.20]( 2) 2 ) = 0.60

(c) µ =
1
2
([0.10](3) 2 + [0.30](1) 2 + [0.20]( 2) 2 + [0.40](1) 2 ) = 1.2

(d) µ =
1
2
([0.060](3) 2 + [0.180](1) 2 + [0.030](2) 2 + [0.060](1) 2 ) = 0.45

µ
2
0.51Z A
10-8 − log γ A =
1 + 3.3α A µ

Z µ µ α -log γ γ
(a) 3 0.075 0.274 0.9 0.693 0.20
(b) 2 0.012 0.110 0.45 0.193 0.64
(c) 4 0.080 0.283 1.1 1.139 0.073
(d) 4 0.060 0.245 1.1 1.058 0.087

10-9

(a)

µ = 0.05 γ Fe3+ = 0.24 µ = 0.10 γ Fe3+ = 0.18

γ Fe3+ (µ = 0.075) = 0.18 +

0.025
(0.24 − 0.18) = 0.21
0.05

(b)

µ = 0.01 γ Pb2 + = 0.665 µ = 0.05 γ Pb2 + = 0.45

γ Pb2+ (µ = 0.012) = 0.45 +

0.038
(0.665 − 0.45) = 0.61
0.05
Fundamentals of Analytical Chemistry: 8th ed. Chapter 10

(c)

µ = 0.05 γ Ce4 + = 0.10 µ = 0.10 γ Ce4 + = 0.063

γ Ce4 + (µ = 0.080) = 0.063 +

0.02
(0.10 − 0.063) = 0.078
0.05

(d)

µ = 0.05 γ Sn4 + = 0.10 µ = 0.10 γ Sn 4+ = 0.063

γ Sn4 + (µ = 0.060) = 0.063 +

0.04
(0.10 − 0.063) = 0.093
0.05

10-10 (a)

µ = 5.0 × 10 −2 γ Ag + = 0.80 γ SCN − = 0.81

K sp 1.1 × 10 −12
K sp = = = 1.7 × 10 −12
'

γ Ag + γ SCN − (0.80)(0.81)

(b)

µ = 5.0 × 10 −2 γ Pb2 + = 0.46 γ I − = 0.80

K sp 7.9 × 10 −9
K sp = = = 2.7 × 10 −8
'

γ Pb2+ γ I − (0.45)(0.80) 2

(c)

µ = 5.0 × 10 −2 γ La 3+ = 0.24 γ IO − = 0.82

3

−11
K sp 1.0 × 10
K sp = = = 7.6 × 10 −11
'

γ La3+ γ IO − (0.24)(0.82) 3
3

(d)

µ = 5.0 × 10 −2 γ Mg2+ = 0.52 γ NH + = 0.80 γ PO 3− = 0.16

4 4

−13
K sp 3.0 × 10
K sp = = = 4.5 × 10 −12
'

γ Mg2+ γ NH + γ PO 3− (0.52)(0.80)(0.16)
4 4
Fundamentals of Analytical Chemistry: 8th ed. Chapter 10

10-11 Zn(OH ) 2 ( s ) →
←
Zn 2+ + 2OH − K sp = 3.0 × 10 −16

(a)

µ=
1
2
(0.0100(1) 2 + 0.0100(1) 2 ) = 0.0100

From Table 10 − 2,
γ Zn2 + = 0.675 γ OH − = 0.90
K ' sp = a Zn2 + aOH − = γ Zn 2+ [ Zn 2+ ] × γ OH − [OH − ]
2 2

3.0 × 10 −16 3.0 × 10 −16

[ Zn 2+ ][OH − ]2 = = = 5.49 × 10 −16
γ Zn2+ γ OH −
2 2
( 0. 675 )( 0 .90 )
1
Solubility = S = [Zn 2+ ] = [OH − ]
2
S( 2S) 2 = 5.49 × 10 −16
1
⎛ 5.49 × 10 −16 ⎞ 3
S = ⎜⎜ ⎟⎟ = 5.2 × 10 −6 M
⎝ 4 ⎠

(b)

µ=
1
2
(( 2 × 0.0167)(1) 2 + 0.0167( 2) 2 ) = 0.050

From Table 10 − 2,
γ Zn2 + = 0.48 γ OH − = 0.81

K ' sp = a Zn2 + aOH − = γ Zn2 + [ Zn 2+ ] × γ OH − [OH − ]

2 2

3.0 × 10 −16 3.0 × 10 −16

[ Zn 2+ ][OH − ]2 = = = 9.53 × 10 −16
γ Zn2+ γ OH −
2 2
(0.48)(0.81)
1
Solubility = S = [Zn 2+ ] = [OH − ]
2
S( 2S) 2 = 9.53 × 10 −16
1
⎛ 9.53 × 10 −16 ⎞ 3
S = ⎜⎜ ⎟⎟ = 6.2 × 10 −6 M
⎝ 4 ⎠
Fundamentals of Analytical Chemistry: 8th ed. Chapter 10

(c)

0.250 mole L
0.25 M KOH ≡ × × 20.0 mL = 5.0 × 10 −3 mole KOH
L 1000 mL
0.0250 mole L
0.0250 M ZnCl 2 ≡ × × 80.0 mL = 2.0 × 10 −3 mole ZnCl 2
L 1000 mL

5.0 × 10 −3 mole 1000 mL

[K + ] = × = 5.0 × 10 −2 M
100.0 mL L

[OH − ] =
(5.0 × 10 −3
− ( 2 × ( 2.0 × 10 −3 )) ) 1000 mL
× = 1.0 × 10 −2 M
100.0 mL L
2 × ( 2.0 × 10 −3 mole) 1000 mL
[Cl − ] = × = 4.0 × 10 −2 M
100.0 mL L
[ Zn 2+ ] = 0

µ=
1
2
(0.05(1) 2 + 0.010(1) 2 + 0.04(1) 2 ) = 0.05

From Table 10 − 2,
γ Zn2 + = 0.48 γ OH − = 0.81 K ' sp = a Zn2 + aOH − = γ Zn2 + [ Zn 2+ ] × γ OH − [OH − ]
2 2

3.0 × 10 −16 3.0 × 10 −16

[ Zn 2+ ][OH − ]2 = = = 9.53 × 10 −16
γ Zn2+ γ OH −
2 2
(0.48)(0.81)
Solubility = S = [Zn 2+ ] S(1.0 × 10 −2 ) 2 = 9.53 × 10 −16
⎛ 9.53 × 10 −16 ⎞
S = ⎜⎜ ⎟ = 9.53 × 10 −12 M
−2 2 ⎟
⎝ (1.0 × 10 ) ⎠

(d)

0.100 mole L
0.100 M KOH ≡ × × 20.0 mL = 2.0 × 10 −3 mole KOH
L 1000 mL
0.0250 mole L
0.0250 M ZnCl 2 ≡ × × 80.0 mL = 2.0 × 10 −3 mole ZnCl 2
L 1000 mL
5.0 × 10 −3 mole 1000 mL
[K + ] = × = 2.0 × 10 −2 M
100.0 mL L
[OH − ] = 0
2 × ( 2.0 × 10 −3 mole) 1000 mL
[Cl − ] = × = 4.0 × 10 −2 M
100.0 mL L
Fundamentals of Analytical Chemistry: 8th ed. Chapter 10

1
2.0 × 10 −3 − ( 2.0 × 10 −3 )
2+ 2 1000 mL
[ Zn ] = × = 1.0 × 10 −2 M
100.0 mL L

µ=
1
2
(0.02(1) 2 + 0.040(1) 2 + 0.01(2) 2 ) = 0.05
From Table 10 − 2,
γ Zn2 + = 0.48 γ OH − = 0.81
K ' sp = a Zn 2+ aOH − = γ Zn2+ [ Zn 2+ ] × γ OH − [OH − ]
2 2

3.0 × 10 −16 3.0 × 10 −16

[ Zn 2+ ][OH − ]2 = = = 9.53 × 10 −16
γ Zn2+ γ OH −
2
(0.48)(0.81) 2
1
Solubility = S = [OH − ]
2
(1.0 × 10 −2 )[OH − ]2 = 9.53 × 10 −16
1
⎛ 9.53 × 10 −16 ⎞ 2
[OH − ] = ⎜⎜ −2 ⎟
⎟ = 3.09 × 10 −7 M
⎝ (1 .0 × 10 ) ⎠
S = (3.09 × 10 −7 M ) = 1.5 × 10 −7 M
1
2

10-12 µ =
1
2
(
0.0333(2 ) + (2 × (0.0333))(1) 2 = 0.100
2
)
(a)

AgSCN( s ) →
←
Ag + + SCN −

(1) γ Ag + = 0.75 γ SCN − = 0.76 K ' sp = a Ag + aSCN − = γ Ag+ [ Ag + ] × γ SCN − [SCN − ]

1.1 × 10 −12 1.1 × 10 −12

[ Ag + ][SCN − ] = = = 1.93 × 10 −12
γ Ag + γ SCN − (0.75)(0.76)
Solubility = S = [Ag + ] = [SCN − ]
S 2 = 1.93 × 10 −12

S = (1.93 × 10 −12 )2 = 1.4 × 10 −6 M

1

1
( 2) S = (1.1 × 10 −12 ) 2 = 1.0 × 10 −6 M
Fundamentals of Analytical Chemistry: 8th ed. Chapter 10

(b)

PbI 2 ( s ) →
←
Pb 2+ + 2I −

γ Pb2 + = 0.36 γ I − = 0.75 K ' sp = a Pb2+ a I − = γ Pb2 + [ Pb 2+ ] × ( γ I − [ I − ]) 2

2
(1)
7.9 × 10 −9 7.9 × 10 −9
[ Pb 2+ ][ I − ]2 = = = 3.90 × 10 −8
γ Pb2 + γ I −
2
(0.36)(0.75) 2
1 −
Solubility = S = [Pb 2+ ] = [I ]
2
S( 2S) 2 = 3.90 × 10 −8
1
⎛ 3.90 × 10 −8 ⎞ 3
S = ⎜⎜ ⎟⎟ = 2.1 × 10 −3 M
⎝ 4 ⎠
7.9 × 10 −9 3
1
( 2) S = ( ) = 1.3 × 10 −3 M
4

(c)

2−
BaSO 4 ( s ) →
←
Ba 2+ + SO 4
2−
(1) γ Ba 2 + = 0.38 γ SO 2− = 0.35 K ' sp = a Ba 2+ aSO 2− = γ Ba 2+ [ Ba 2+ ] × γ SO 2 − [SO 4 ]
4 4 4

2− 1.1 × 10 −10 1.1 × 10 −10

[ Ba 2+ ][SO 4 ] = = = 8.3 × 10 −10
γ Ba 2 + γ SO 2− (0.38)(0.35)
4

2+ 2−
Solubility = S = [Ba ] = [SO 4 ]
S 2 = 8.3 × 10 −10

S = (8.3 × 10 −10 )2 = 2.9 × 10 −5 M

1

1
−10 2
( 2) S = (1.1 × 10 ) = 1.0 × 10 −5 M
Fundamentals of Analytical Chemistry: 8th ed. Chapter 10

(d)

4−
Cd 2 Fe(CN ) 6 ( s ) →
←
2Cd 2+ + Fe(CN ) 6
(1) γ Cd2 + = 0.38 γ Fe ( CN ) 4 − = 0.020
6

4−
K ' sp = aCd 2+ a Fe ( CN ) 4− = ( γ Cd 2+ [Cd 2+ ]) 2 × γ Fe ( CN ) 4 − [ Fe(CN ) 6 ]
2
6 6

4− 3.2 × 10 −17 3.2 × 10 −17

[Cd 2+ ]2 [ Fe(CN ) 6 ] = = = 1.1 × 10 −13
γ Cd2 + γ Fe ( CN ) 4 − (0.38) (0.020)
2 2
6

1 4−
Solubility = S = [Cd 2+ ] = [ Fe(CN ) 6 ]
2
( 2S) S = 1.1 × 10 −13
2

1
⎛ 1.1 × 10 −13 ⎞ 3
S = ⎜⎜ ⎟⎟ = 1.4 × 10 −5 M
⎝ 4 ⎠
3.2 × 10 −17 3
1
( 2) S = ( ) = 2.0 × 10 −6 M
4

10-13 µ =
1
2
(
0.0167(2 ) + (2 × (0.0167 ))(1) 2 = 0.050
2
)
(a)

−
AgIO 3 ( s ) →
←
Ag + + IO 3
−
(1) γ Ag + = 0.80 γ IO − = 0.82 K ' sp = a Ag + a IO − = γ Ag+ [ Ag + ] × γ IO − [ IO 3 ]
3 3 3

− 3.1 × 10 −8 3.1 × 10 −8
[ Ag + ][ IO 3 ] = = = 4.7 × 10 −8
γ Ag+ γ IO − (0.80)(0.82)
3

+ −
Solubility = S = [Ag ] = [ IO 3 ]
S 2 = 4.7 × 10 −8

S = (4.7 × 10 −8 )2 = 2.2 × 10 −4 M
1

1
( 2) S = (3.1 × 10 ) = 1.8 × 10 −4 M
−8 2
Fundamentals of Analytical Chemistry: 8th ed. Chapter 10

(b)

Mg(OH ) 2 ( s ) →
←
Mg 2+ + 2OH −

γ Mg2+ = 0.52 γ OH − = 0.81 K ' sp = a Mg2+ aOH − = γ Mg2+ [ Mg 2+ ] × ( γ OH − [OH − ]) 2

2
(1)

7.1 × 10 −12 7.1 × 10 −12

[ Mg 2+ ][OH − ]2 = = = 2.1 × 10 −11
γ Mg2+ γ OH −
2 2
(0.52)(0.81)
1
Solubility = S = [Mg 2+ ] = [OH − ]
2
S( 2S) 2 = 2.1 × 10 −11
1
⎛ 2.1 × 10 −11 ⎞ 3
S = ⎜⎜ ⎟⎟ = 1.7 × 10 −4 M
⎝ 4 ⎠
7.1 × 10 −12 3
1
( 2) S = ( ) = 1.2 × 10 −4 M
4

(c)

2−
BaSO 4 ( s ) →
←
Ba 2+ + SO 4
2−
(1) γ Ba 2+ = 0.46 γ SO 2 − = 0.44 K ' sp = a Ba 2+ aSO 2− = γ Ba 2 + [ Ba 2+ ] × γ SO 2− [SO 4 ]
4 4 4

2− 1.1 × 10 −10 1.1 × 10 −10

[ Ba 2+ ][SO 4 ] = = = 5.4 × 10 −10
γ Ba 2 + γ SO 2 − (0.46)(0.44)
4

2−
Solubility = S = [SO 4 ]
(0.0167 M ) × S = 5.4 × 10 −10
⎛ 5.4 × 10 −10 ⎞
S = ⎜⎜ ⎟⎟ = 3.3 × 10 −8 M
⎝ 0 .0167 ⎠
⎛ 1.1 × 10 −10 ⎞
( 2) S = ⎜⎜ ⎟⎟ = 6.6 × 10 −9 M
⎝ 0. 0167 ⎠
Fundamentals of Analytical Chemistry: 8th ed. Chapter 10

(d)

−
La ( IO 3 ) 3 ( s ) →
←
La 3+ + 3IO 3
−
γ La3+ = 0.24 γ IO − = 0.82 K ' sp = a La3+ a IO − = γ La 3+ [ La 3+ ] × ( γ IO − [ IO 3 ]) 3
3
(1)
3 3 3

− 1.0 × 10 −11 1.0 × 10 −11

[ La 3+ ][ IO 3 ]3 = = = 7.6 × 10 −11
γ La3+ γ IO −
3 3
(0.24)(0.82)
3

1 −
Solubility = S = [La 3+ ] = [ IO 3 ]
3

S(3S) 3 = 7.6 × 10 −11

1
⎛ 7.6 × 10 −11 ⎞ 4
S = ⎜⎜ ⎟⎟ = 1.3 × 10 −3 M
⎝ 27 ⎠
1
⎛ 1.0 × 10 −11 ⎞ 4
( 2) S = ⎜⎜ ⎟⎟ = 7.8 × 10 −4 M
⎝ 27 ⎠

10-14 µ =
1
2
(
0.05000(1) + 0.05000(1) 2 = 0.050
2
)

(a) CuCl( s ) →
←
Cu + + Cl −

If we assume that Cu+ has an effective diameter of 0.3 like similarly charged cations, then

(1) γ Cu + = 0.80 γ Cl− = 0.80 K ' sp = aCu + aCl− = γ Cu + [Cu + ] × γ Cl− [Cl − ]
+ 1.9 × 10 −7
− 1.9 × 10 −7
[Cu ][Cl ] = = = 2.97 × 10 −7
γ Cu + γ Cl2− (0.80)(0.80)
Solubility = S = [Cu + ] = [Cl − ]
S 2 = 2.97 × 10 −7

S = (2.97 × 10 −7 )2 = 5.4 × 10 −4 M
1

( 2) S = (1.9 × 10 −7 )2 = 4.4 × 10 −4 M
1

relative error =
(4.4 × 10 −4
− 5.4 × 10 −4 )
× 100% = − 19%
5.4 × 10 −4
Fundamentals of Analytical Chemistry: 8th ed. Chapter 10

(b)

Fe(OH ) 2 ( s ) →
←
Fe 2+ + 2OH −

γ Fe2+ = 0.48 γ OH − = 0.81 K ' sp = a Fe2 + aOH − = γ Fe2 + [ Fe 2+ ] × ( γ OH − [OH − ]) 2

2
(1)
4.1 × 10 −15 4.1 × 10 −15
[ Fe 2+ ][OH − ]2 = = = 1.3 × 10 −14
γ Fe2 + γ OH −
2
(0.48)(0.81) 2
1
Solubility = S = [Fe 2+ ] = [OH − ]
2
S( 2S) 2 = 1.3 × 10 −14

1
⎛ 1.3 × 10 −14 ⎞ 3
S = ⎜⎜ ⎟⎟ = 1.6 × 10 −5 M
⎝ 4 ⎠
1
⎛ 4.1 × 10 −15 ⎞ 3
( 2) S = ⎜⎜ ⎟⎟ = 1.1 × 10 −5 M
⎝ 4 ⎠
1.1 × 10 −5 − 1.6 × 10 −5
relative error = × 100% = − 31%
1.6 × 10 −5

(c)

Fe(OH ) 3 ( s ) →
←
Fe 3+ + 3OH −

γ Fe3+ = 0.24 γ OH − = 0.81 K ' sp = a Fe3+ aOH − = γ Fe3+ [ Fe 3+ ] × ( γ OH − [OH − ]) 3

3
(1)

2 × 10 −39 2 × 10 −39
[ Fe 3+ ][OH − ]3 = = = 2 × 10 −38
γ Fe3+ γ OH −
3 3
(0.24)(0.81)
1
Solubility = S = [Fe 3+ ] = [OH − ]
3
− 38
S(3S) = 2 × 10
3

1
⎛ 2 × 10 −38 ⎞ 4
S = ⎜⎜ ⎟⎟ = 1.55 × 10 −10 M
⎝ 27 ⎠
1
⎛ 2 × 10 −39 ⎞ 4
( 2) S = ⎜⎜ ⎟⎟ = 9.3 × 10 −11 M
⎝ 27 ⎠
9.3 × 10 −11 − 1.55 × 10 −10
relative error = × 100% = − 40%
1.55 × 10 −10
Fundamentals of Analytical Chemistry: 8th ed. Chapter 10

(d)

−
La ( IO 3 ) 3 ( s ) →
←
La 3+ + 3IO 3
−
γ La3+ = 0.24 γ IO − = 0.82 K ' sp = a La3+ a IO − = γ La 3+ [ La 3+ ] × ( γ IO − [ IO 3 ]) 3
3
(1)
3 3 3

− 1.0 × 10 −11 1.0 × 10 −11

[ La 3+ ][ IO 3 ]3 = = = 7.6 × 10 −11
γ La3+ γ IO −
3 3
(0.24)(0.82)
3

1 −
Solubility = S = [La 3+ ] = [ IO 3 ]
3

S(3S) 3 = 7.6 × 10 −11

1
⎛ 7.6 × 10 −11 ⎞ 4
S = ⎜⎜ ⎟⎟ = 1.3 × 10 −3 M
⎝ 27 ⎠
1
⎛ 1.1 × 10 −11 ⎞ 4
( 2) S = ⎜⎜ ⎟⎟ = 8.0 × 10 −4 M
⎝ 27 ⎠
8.0 × 10 −4 − 1.3 × 10 −3
relative error = × 100% = − 38%
1.3 × 10 −3

3−
(e) Ag 3 ( AsO 4 )( s ) →
←
3Ag + + AsO 4

If we assume that AsO43- has an effective diameter of 0.4 like similarly charged anions,

then

3−
γ Ag + = 0.80 γ AsO 3− = 0.16 K ' sp = a Ag + a AsO 3− = ( γ Ag + [ Ag + ]) 3 × γ AsO 3− [ AsO 4 ]
3
(1)
4 4 4

+ 3 3− 6 × 10 −23 6 × 10 −23
[ Ag ] [ AsO 4 ]= = = 7.3 × 10 −22
γ Ag + γ AsO 3− (0.80) (0.16)
3 3
4

4− 1
Solubility = S = [AsO 3 ] = [ Ag + ]
3
Fundamentals of Analytical Chemistry: 8th ed. Chapter 10

(3S) 3 S = 2.9 × 10 −22

1
⎛ 7.3 × 10 −22 ⎞ 4
S = ⎜⎜ ⎟⎟ = 2.3 × 10 −6 M
⎝ 27 ⎠
1
⎛ 6 × 10 −23 ⎞ 4
( 2) S = ⎜⎜ ⎟⎟ = 1.2 × 10 −6 M
⎝ 27 ⎠
1.2 × 10 −6 − 2.3 × 10 −6
relative error = × 100% = − 46%
2.3 × 10 −6

10-15 (a) µ =
1
2
(
0.200(1) + 0.200(1) 2 = 0.200
2
)
(0.51)(1) 2 0.20
− log γ H O+ = = 0.0979 γ H O+ = 0.798
3
1 + (3.3)(0.9) 0.20 3

(0.51)(1) 2 0.20
− log γ OAc − = = 0.140 γ OAc− = 0.724
1 + (3.3)(0.425) 0.20
γ H O+ [ H 3O + ]γ OAc − [OAc − ]
K 'a = 3
= γ H O+ γ OAc − K a = (0.798)(0.724)(1.75 × 10 −5 ) = 1.01 × 10 −5
[ HOAc] 3

[ H 3O + ] = (1.01 × 10 −5 )(0.10) = 1.00 × 10 −3 M

[ H 3O + ] = (1.75 × 10 −5 )(0.10) = 1.32 × 10 −3 M
1.32 × 10 −3 − 1.0 × 10 −3
relative error = × 100% = 32%
1.0 × 10 −3

(b) µ =
1
2
( 2
)
0.200(1) + 0.200(1) 2 = 0.200

(0.51)(1) 2 0.20
− log γ NH + = = 0.167 γ H O+ = 0.681
4
1 + (3.3)(0.25) 0.20 3

(0.51)(1) 2 0.20
− log γ OH − = = 0.150 γ OAc − = 0.708
1 + (3.3)(0.35) 0.20
Fundamentals of Analytical Chemistry: 8th ed. Chapter 10

+
γ NH + [ NH 4 ]γ OH − [OH − ] ⎛ 1.0 × 10 −14 ⎞
K 'b = 4
= γ NH + γ OH − K b = (0.681)(0.708)⎜⎜ ⎟ = 9.32 × 10 −6
−10 ⎟
[ NH 3 ] 4
⎝ 5.70 × 10 ⎠
−14
1.0 × 10
[OH − ] = (9.32 × 10 −6 )(0.050) = 6.83 × 10 −4 M [ H 3O + ] = = 1.46 × 10 −11 M
6.83 × 10 −4
1.0 × 10 −14
[OH − ] = (1.75 × 10 −5 )(0.050) = 9.36 × 10 −4 M [ H 3O + ] = −4
= 1.07 × 10 −11 M
9.36 × 10
−11 −11
1.07 × 10 − 1.46 × 10
relative error = × 100% = 27%
1.46 × 10 −11

(c)

µ=
1
2
(
0.0600(1) + 0.0600(1) 2 = 0.060
2
)
(0.51)(1) 2 0.060
− log γ H O+ = = 0.07232 γ H O+ = 0.847
3
1 + (3.3)(0.9) 0.060 3

(0.51)(1) 2 0.060
− log γ ClCH COO− = = 0.0930 γ ClCH COO− = 0.807
2
1 + (3.3)(0.425) 0.060 2

γ H O+ [ H 3O + ]γ OAc− [ClCH 2 COO − ]

K 'a = 3
= γ H O+ γ ClCH COO− K a
[ClCH 2 COOH ] 3 2

= (0.847)(0.807)(1.36 × 10 −3 ) = 9.30 × 10 −4
[ H 3O + ] = (9.3 × 10 −4 )(0.01) = 3.05 × 10 −3 M
[ H 3O + ] = (1.36 × 10 −3 )(0.01) = 3.69 × 10 −3 M
3.69 × 10 −3 − 3.05 × 10 −3
relative error = × 100% = 21%
3.05 × 10 −3
Fundamentals of Analytical Chemistry: 8th ed. Chapter 10

10-16

A B C D E F G H I
1 Problem 10-16(a)
2
3 Ksp(AgIO3)
4 3.10E-08
5
µ γ(Ag ) γ(IO3 )
+ -
6 c(Ba(NO3)2) pc(Ba(NO3)2) s(conc) ps(conc) s(act) ps(act)
7 0.0001 4.00 1.76E-04 3.75 1.81E-04 3.74 4.76E-04 0.975 0.975
8 0.0002 3.70 1.76E-04 3.75 1.82E-04 3.74 7.76E-04 0.969 0.969
9 0.0004 3.40 1.76E-04 3.75 1.84E-04 3.74 1.38E-03 0.959 0.959
10 0.0008 3.10 1.76E-04 3.75 1.86E-04 3.73 2.58E-03 0.944 0.946
11 0.001 3.00 1.76E-04 3.75 1.87E-04 3.73 3.18E-03 0.939 0.941
12 0.002 2.70 1.76E-04 3.75 1.92E-04 3.72 6.18E-03 0.917 0.920
13 0.004 2.40 1.76E-04 3.75 1.98E-04 3.70 1.22E-02 0.888 0.894
14 0.008 2.10 1.76E-04 3.75 2.06E-04 3.69 2.42E-02 0.851 0.861
15 0.01 2.00 1.76E-04 3.75 2.09E-04 3.68 3.02E-02 0.837 0.849
16 0.02 1.70 1.76E-04 3.75 2.21E-04 3.66 6.02E-02 0.787 0.807
17 0.04 1.40 1.76E-04 3.75 2.37E-04 3.63 1.20E-01 0.729 0.760
18 0.08 1.10 1.76E-04 3.75 2.56E-04 3.59 2.40E-01 0.664 0.711
19 0.1 1.00 1.76E-04 3.75 2.64E-04 3.58 3.00E-01 0.642 0.695
20 0.2 0.70 1.76E-04 3.75 2.89E-04 3.54 6.00E-01 0.574 0.647
21 0.4 0.40 1.76E-04 3.75 3.18E-04 3.50 1.20E+00 0.509 0.602
22 0.8 0.10 1.76E-04 3.75 3.50E-04 3.46 2.40E+00 0.450 0.564
23 1 0.00 1.76E-04 3.75 3.60E-04 3.44 3.00E+00 0.433 0.553
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39 Spreadsheet Documentation
40 B7=-LOG(A7) F7=-LOG(E7)
41 C7=SQRT(A$4) G7=0.5((A7)*(2)*(2)+(2*A7)*(1)*(1)+(C7)*(1)*(1)+(C7)*(-1)*(-1))
42 D7=-LOG(C7) H7=10^(-0.51*(1)*(1)*SQRT(G7)/(1+(3.3*0.25*SQRT(G7)))
43 E7=SQRT(A$4/(H7*I7)) I7=10^(-0.51*(-1)*(-1)*SQRT(G7)/(1+(3.3*0.425*SQRT(G7)))
Fundamentals of Analytical Chemistry: 8th ed. Chapter 10

A B C D E F G H I
1 Problem 10-16(b)
2
3 Ksp(Mg(OH)2)
4 7.10E-12
5
µ γ(Mg ) γ(OH )
2+ -
6 c(Ba(NO3)2) pc(Ba(NO3)2) s(conc) ps(conc) s(act) ps(act)
7 0.0001 4.00 1.21E-04 3.92 1.30E-04 3.88 1.13E-03 0.865 0.963
8 0.0002 3.70 1.21E-04 3.92 1.32E-04 3.88 1.53E-03 0.847 0.957
9 0.0004 3.40 1.21E-04 3.92 1.34E-04 3.87 2.33E-03 0.818 0.948
10 0.0008 3.10 1.21E-04 3.92 1.38E-04 3.86 3.93E-03 0.777 0.934
11 0.001 3.00 1.21E-04 3.92 1.39E-04 3.86 4.73E-03 0.761 0.928
12 0.002 2.70 1.21E-04 3.92 1.45E-04 3.84 8.73E-03 0.703 0.906
13 0.004 2.40 1.21E-04 3.92 1.54E-04 3.81 1.67E-02 0.636 0.876
14 0.008 2.10 1.21E-04 3.92 1.65E-04 3.78 3.27E-02 0.563 0.839
15 0.01 2.00 1.21E-04 3.92 1.69E-04 3.77 4.07E-02 0.539 0.825
16 0.02 1.70 1.21E-04 3.92 1.85E-04 3.73 8.07E-02 0.466 0.778
17 0.04 1.40 1.21E-04 3.92 2.04E-04 3.69 1.61E-01 0.401 0.725
18 0.08 1.10 1.21E-04 3.92 2.26E-04 3.65 3.21E-01 0.344 0.669
19 0.1 1.00 1.21E-04 3.92 2.34E-04 3.63 4.01E-01 0.329 0.651
20 0.2 0.70 1.21E-04 3.92 2.59E-04 3.59 8.01E-01 0.286 0.596
21 0.4 0.40 1.21E-04 3.92 2.86E-04 3.54 1.60E+00 0.254 0.547
22 0.8 0.10 1.21E-04 3.92 3.12E-04 3.51 3.20E+00 0.230 0.504
23 1 0.00 1.21E-04 3.92 3.20E-04 3.49 4.00E+00 0.224 0.492
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39 Spreadsheet Documentation
40 B7=-LOG(A7) F7=-LOG(E7)
41 C7=(A$4/(4))^(1/3) G7=0.5((A7)*(2)*(2)+(2*A7)*(-1)*(-1)+(C7)*(2)*(2)+(2*C7)*(-1)*(-1))
42 D7=-LOG(C7) H7=10^(-0.51*(2)*(1)*SQRT(G7)/(1+(3.3*0.80*SQRT(G7)))
43 E7=(A$4/(4*H7*I7*I7))^(1/3) I7=10^(-0.51*(-1)*(-1)*SQRT(G7)/(1+(3.3*0.35*SQRT(G7)))
Fundamentals of Analytical Chemistry: 8th ed. Chapter 10

A B C D E F G H I
1 Problem 10-16(c)
2
3 Ksp(BaSO4)
4 1.10E-10
5
µ γ(Ba ) γ(SO4 )
2+ 2-
6 c(Ba(NO3)2) pc(Ba(NO3)2) s(conc) ps(conc) s(act) ps(act)
7 0.0001 4.00 1.10E-06 5.96 1.32E-06 5.88 4.09E-04 0.912 0.912
8 0.0002 3.70 5.50E-07 6.26 7.10E-07 6.15 8.04E-04 0.880 0.879
9 0.0004 3.40 2.75E-07 6.56 3.92E-07 6.41 1.60E-03 0.838 0.836
10 0.0008 3.10 1.38E-07 6.86 2.25E-07 6.65 3.20E-03 0.784 0.781
11 0.001 3.00 1.10E-07 6.96 1.89E-07 6.72 4.00E-03 0.764 0.760
12 0.002 2.70 5.50E-08 7.26 1.15E-07 6.94 8.00E-03 0.693 0.687
13 0.004 2.40 2.75E-08 7.56 7.48E-08 7.13 1.60E-02 0.612 0.601
14 0.008 2.10 1.38E-08 7.86 5.19E-08 7.28 3.20E-02 0.523 0.507
15 0.01 2.00 1.10E-08 7.96 4.69E-08 7.33 4.00E-02 0.493 0.476
16 0.02 1.70 5.50E-09 8.26 3.58E-08 7.45 8.00E-02 0.404 0.380
17 0.04 1.40 2.75E-09 8.56 2.92E-08 7.54 1.60E-01 0.322 0.292
18 0.08 1.10 1.38E-09 8.86 2.49E-08 7.60 3.20E-01 0.253 0.218
19 0.1 1.00 1.10E-09 8.96 2.38E-08 7.62 4.00E-01 0.234 0.198
20 0.2 0.70 5.50E-10 9.26 2.06E-08 7.69 8.00E-01 0.183 0.146
21 0.4 0.40 2.75E-10 9.56 1.74E-08 7.76 1.60E+00 0.146 0.108
22 0.8 0.10 1.38E-10 9.86 1.40E-08 7.85 3.20E+00 0.119 0.082
23 1 0.00 1.10E-10 9.96 1.29E-08 7.89 4.00E+00 0.113 0.076
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39 Spreadsheet Documentation
40 B7=-LOG(A7) F7=-LOG(E7)
41 C7=(A$4/(A7)) G7=0.5((A7)*(2)*(2)+(2*A7)*(1)*(1))
42 D7=-LOG(C7) H7=10^(-0.51*(2)*(2)*SQRT(G7)/(1+(3.3*0.50*SQRT(G7)))
43 E7=(A$4/(A7*H7*I7)) I7=10^(-0.51*(-2)*(-2)*SQRT(G7)/(1+(3.3*0.40*SQRT(G7)))
Fundamentals of Analytical Chemistry: 8th ed. Chapter 10

A B C D E F G H I
1 Problem 10-16(d)
2
3 Ksp(La(IO3)3
4 1.00E-11
5
µ γ(La ) γ(IO3 )
3+ -
6 c(Ba(NO3)2) pc(Ba(NO3)2) s(conc) ps(conc) s(act) ps(act)
7 0.0001 4.00 7.80E-04 3.11 9.63E-04 3.02 4.98E-03 0.540 0.927
8 0.0002 3.70 7.80E-04 3.11 9.69E-04 3.01 5.28E-03 0.532 0.925
9 0.0004 3.40 7.80E-04 3.11 9.78E-04 3.01 5.88E-03 0.517 0.921
10 0.0008 3.10 7.80E-04 3.11 9.96E-04 3.00 7.08E-03 0.491 0.915
11 0.001 3.00 7.80E-04 3.11 1.00E-03 3.00 7.68E-03 0.480 0.912
12 0.002 2.70 7.80E-04 3.11 1.04E-03 2.98 1.07E-02 0.434 0.899
13 0.004 2.40 7.80E-04 3.11 1.10E-03 2.96 1.67E-02 0.373 0.878
14 0.008 2.10 7.80E-04 3.11 1.19E-03 2.93 2.87E-02 0.304 0.850
15 0.01 2.00 7.80E-04 3.11 1.22E-03 2.91 3.47E-02 0.282 0.839
16 0.02 1.70 7.80E-04 3.11 1.35E-03 2.87 6.47E-02 0.216 0.800
17 0.04 1.40 7.80E-04 3.11 1.52E-03 2.82 1.25E-01 0.162 0.754
18 0.08 1.10 7.80E-04 3.11 1.72E-03 2.76 2.45E-01 0.120 0.704
19 0.1 1.00 7.80E-04 3.11 1.80E-03 2.75 3.05E-01 0.110 0.687
20 0.2 0.70 7.80E-04 3.11 2.03E-03 2.69 6.05E-01 0.083 0.637
21 0.4 0.40 7.80E-04 3.11 2.29E-03 2.64 1.20E+00 0.066 0.591
22 0.8 0.10 7.80E-04 3.11 2.54E-03 2.60 2.40E+00 0.054 0.550
23 1 0.00 7.80E-04 3.11 2.61E-03 2.58 3.00E+00 0.051 0.538
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39 Spreadsheet Documentation
40 B7=-LOG(A7) F7=-LOG(E7)
41 C7=(A$4/(A7)) G7=0.5((A7)*(2)*(2)+(2*A7)*(-1)*(-1)+(C7)*(3)*(3)+(3*C7)*(-1)*(-1))
42 D7=-LOG(C7) H7=10^(-0.51*(3)*(3)*SQRT(G7)/(1+(3.3*0.90*SQRT(G7)))
43 E7=(A$4/(27*H7*I7^3))^(1/4) I7=10^(-0.51*(-1)*(-1)*SQRT(G7)/(1+(3.3*0.40*SQRT(G7)))
Fundamentals of Analytical Chemistry: 8th ed. Chapter 10

10-17

A B C D E F G
1 Problem 10-17
2
3 µ
4 αx Z 0.001 0.005 0.01 0.05 0.1
5 0.9 1 0.967 0.934 0.913 0.854 0.826
6 0.6 1 0.966 0.930 0.907 0.834 0.796
7 0.425 1 0.965 0.927 0.902 0.819 0.773
8 0.35 1 0.965 0.926 0.900 0.812 0.762
9 0.3 1 0.965 0.925 0.899 0.807 0.754
10 0.25 1 0.964 0.925 0.897 0.801 0.745
11 0.8 2 0.872 0.756 0.690 0.517 0.445
12 0.6 2 0.870 0.747 0.676 0.483 0.401
13 0.5 2 0.868 0.743 0.668 0.464 0.377
14 0.45 2 0.868 0.740 0.664 0.455 0.364
15 0.4 2 0.867 0.738 0.660 0.444 0.351
16 0.9 3 0.737 0.539 0.443 0.242 0.178
17 0.4 3 0.726 0.505 0.393 0.161 0.095
18 1.1 4 0.587 0.347 0.252 0.098 0.063
19 0.5 4 0.569 0.304 0.199 0.046 0.020
20
21 Spreadsheet Documentation
22 C5=10^(-0.51*$B5^2*SQRT(C$4)/(1+3.3*$A5*SQRT(C$4)))