Skoog Fac 10e Sag Ch08

Solution and Answer Guide
Solution and Answer Guide: Skoog et al., Fundamentals of Analytical Chemistry, 10e,
© 2022, 978-0-357-45039-0, Chapter 8: Effect of Electrolytes on Chemical Equilibria
Chapter 8
*8-1. Make a distinction between
Answers:
(a) activity and activity coefficient.
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) thermodynamic and concentration equilibrium constants.

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 on molar
concentrations of reactants and products as well as other chemical species that
may not participate in the equilibrium.
8-2. List several general properties of activity coefficients.
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.
*8-3. Neglecting any effects caused by volume changes, would you expect the ionic strength to
(1) increase, (2) decrease, or (3) remain essentially unchanged when NaOH is added to a
dilute solution of
Answers:
(a) magnesium chloride [ Mg ( OH)2 ( s ) ] forms?
MgCl2 + 2NaOH  Mg(OH)2 (s) + 2NaCl

Replacing divalent Mg2+ with Na+ causes the ionic strength to decrease.
*Answers and solutions are provided in the Student Solutions Manual for questions and problems marked with an asterisk.
© 2022 Cengage. All Rights Reserved. May not be scanned, copied or duplicated, or posted to a
publicly accessible website, in whole or in part.
1
(b) hydrochloric acid?
HCl + NaOH  H2O + NaCl

There is no change in the charge states of the ions present in the solution
equilibria. The ionic strength is unchanged.
(c) acetic acid?
HOAc + NaOH  H2O + NaOAc

The ionic strength will increase because NaOH and NaOAc are totally ionized
wheras acetic acid is only partially ionized.
8-4. Neglecting any effects caused by volume changes, would you expect the ionic strength to
(1) increase, (2) decrease, or (3) remain essentially unchanged by the addition of iron(III)
chloride to
Answers:
(a) HCl?
The ionic strength will increase when FeCl3 is added to HCl.
(b) NaOH?
3NaOH + FeCl3  Fe(OH)3 (s) + 3NaCl

Addition of FeCl3 to NaOH replaces a univalent OH− with univalent Cl−; thus, the
ionic strength is unchanged.
(c) AgNO3 ?
3AgNO3 + FeCl3  Fe(NO3 )3 + 3AgCl(s)

Addition of FeCl3 replaces the univalent Ag+ with the trivalent Fe3+; thus, the ionic
strength increases.
*8-5. Explain why the activity coefficient for dissolved ions in water is usually less than that for
water itself.
Answer:
Water is a neutral molecule and its activity equals its concentration at all low to
moderate ionic strengths. That is, its activity coefficient is unity. In solutions of low to
moderate ionic strength, activity coefficients of ions decrease with increasing ionic
strength because the ionic atmosphere surrounding the ion causes it to lose some of its
chemical effectiveness and its activity is less than its concentration.
2
8-6. Explain why the activity coefficient for a neutral molecule is usually 1.
Answer:
There is no ionic atmosphere surrounding a neutral molecule and so its activity does not
change with increasing ionic strength. Hence, its activity coefficient is essentially unity
and its activity is equal to its concentration.
*8-7. Explain why the initial slope for Ca2+ in Figure 8-3 is steeper than that for K+?
Answer:
Multiply charged ions deviate from ideality more than singly charged ions because of the
effect of the surrounding ionic atmosphere. The initial slope of the activity coefficient vs
square root of ionic strength for Ca2+ is steeper than that for K+ because the activity
coefficient of Ca2+ is more influenced by ionic strength than that for K+.
8-8. What is the numerical value of the activity coefficient of aqueous ammonia (NH3 ) at an
ionic strength of 0.2?
Answer:
Ammonia (NH3) is an uncharged molecule and thus its activity coefficient is unity.
8-9. Calculate the ionic strength of a solution that is
Solutions:
*(a) 0.025 M in FeSO4 .
μ = ½[0.025 × 22 + 0.025 × 22] = 0.10
(b) 0.25 M in (NH4 )2 CrO4 .
μ = ½[0.50 × 12 + 0.25 × 22] = 0.75
*(c) 0.25 M in FeCl3 and 0.15 M in FeCl2 .
μ = ½[0.25 × 32 + 0.75 × 12 + 0.15 × 22 + 0.30 × 12] = 1.95
(d) 0.025 M in La (NO3 )3 and 0.050 M in Fe (NO3 )2 .
μ = ½[0.025 × 32 + 0.075 × 12 + 0.05 × 22 + 0.10 × 12] = 0.30
3
8-10. Use Equation 8-5 to calculate the activity coefficient of
0.51Z X2 μ
− log γ X = This problem is easiest to work with a spreadsheet.
1 + 3.3α X μ
Rounding these results, gives for the γ X

Solutions:
*(a) Fe31 at μ = 0.057.
0.23
(b) Pb21 at μ = 0.026.
0.54
*(c) Ce41 at μ = 0.065.
0.08
(d) Sn41 at μ = 0.040.
0.11
8-11. Calculate activity coefficients for the species in Problem 8-10 by linear interpolation of
the data in Table 8-2.
Solutions:
(a) μ = 0.05 γ Fe3+ = 0.24 μ = 0.10 γ Fe = 0.18
3+
0.043
γ Fe ( μ = 0.057) = 0.18 +
3+
0.05
( 0.24 − 0.18 ) = 0.23
4
(b) μ = 0.01 γ Pb = 0.665 μ = 0.05 γ Pb = 0.45

2+ 2+
0.024
γ Pb ( μ = 0.026) = 0.45 +
2+
0.05
( 0.665 − 0.45 ) = 0.55
(c) μ = 0.05 γ Ce = 0.10 μ = 0.10 γ Ce = 0.063

4+ 4+
0.035
γ Ce ( μ = 0.065) = 0.063 +
4+
0.05
( 0.10 − 0.063 ) = 0.088 ≈ 0.09
(d) μ = 0.01 γ Sn = 0.252 μ = 0.05 γ Sn = 0.10

4+ 4+
0.01
γ Sn ( μ = 0.040) = 0.10 +
4+
0.05
( 0.252 − 0.10 ) = 0.13
8-12. For a solution in which μ = 6.5 × 10−2 , calculate K sp

′ for
Solutions:
*(a) AgSCN.
0.51Z X2 μ
We must use − log γ X =
1 + 3.3α X μ
For Ag+, α Ag+ = 0.25. At μ = 0.065, γ Ag+ = 0.7809; For SCN−, αSCN − = 0.35 and
γ SCN = 0.7935 retaining insignificant figures for later calculations.
−
K sp 1.1 × 10−12
K sp
′ = = = 1.8 × 10−12
γ Ag γ SCN
+ − (0.7809)(0.7935)
(b) PbI2 .
γ Pb = 0.4195.
For Pb2+, For I−, γ I− = 0.7874
2+
K sp 7.9 × 10−9
K sp
′ = = = 3.0 × 10−8
γ Pb γ I
2+ − (0.4195)(0.7874)2
*(c) La (IO3 )3 .
For La3+, γ La3+ = 0.2158. For IO3−, γ IO − = 0.7935

3
K sp 1.0 × 10 −11
K sp
′ = = = 9.3 × 10 −11
γ La γ IO
3+ − (0.2158)(0.7935)3
3
5
(d) MgNH4PO4 .
For Mg2+, γ = 0.4888; for NH4+, γ = 0.7809; for PO43−, γ = 0.1332

K sp 3.0 × 10 −13
K sp
′ = = = 5.9 × 10 −12
γ Mg2+ γ NH + γ PO 3− (0.4888)(0.7809)(0.1332)
4 4
*8-13. Use activities to calculate the molar solubility of Zn ( OH)2 in
Solutions:
(a) 0.0150 M KCl.
Zn(OH)2(s)  Zn2+ + 2OH− Ksp = 3.0 × 10−16

μ = ½[0.015 × 12 + 0.015 × 12] = 0.0150
Using Equation 8-5,
γ Zn2+ = 0.6294 γ OH− = 0.8816
K sp 2
′ = aZn2+ aOH− = γ
Zn2+
[Zn2+ ] × γ OH
2
− [OH ]
− 2
3.0 × 10 −16 3.0 × 10 −16

[Zn2 + ][OH− ]2 = = = 6.133 × 10−16
2
γ Zn γ OH
2+ − (0.6294)(0.8816)2
Solubility = S = [Zn2+] = ½[OH−]

S(2S)2 = 6.133 × 10−16
1/3
 6.133 × 10 −16 
S =  = 5.35 × 10−6 M
 4 
(b) 0.0250 M K 2 SO4 .
μ = ½[2 × 0.0250 × 12 + 0.0250 × 22] = 0.15/2 = 0.075

From Equation 8-5,
γ Zn = 0.434
2+ γ OH = 0.783
−
K sp 2
′ = aZn2+ aOH− = γ
Zn2+
[Zn2+ ] × γ OH
2
− [OH ]
− 2
3.0 × 10−16
[Zn2+ ][OH− ]2 = = 1.127 × 10−15
(0.434)(0.783)2
Solubility = S = [Zn2+] = ½[OH−]

S(2S)2 = 1.127 × 10−15
1
 1.127 × 10 −15  3
S =  = 6.6 × 10 M
−6
 4 
6
(c) the solution that results when you mix 40.0 mL of 0.250 M KOH with 60.0 mL of
0.0250 M ZnCl2 .
0.250 mmol
amount of KOH = × 40.0 mL = 10.0 mmol
mL
0.0250 mmol
amount of ZnCl2 = × 60.0 mL = 1.5 mmol
mL
10 mmol
[K + ] = = 0.10 M
100.0 mL
[OH− ] =
(10 mmol − (2 × 1.5 mmol) ) = 0.07 M
100.0 mL
2 × 1.5 mmol
[Cl− ] = = 0.03 M
100.0 mL
[Zn2+ ] = 0
μ = ½[0.10 × 12 + 0.07 × 12 + 0.03 × 12] = 0.10
From Table 8-2,
γ Zn = 0.40
2+ γ OH = 0.76
−
2
′ = aZn2+ aOH
K sp − = γ
Zn2+
[Zn2+ ] × γ OH
2
− [OH ]
− 2
3.0 × 10 −16 3.0 × 10 −16

[Zn2+ ][OH− ]2 = = = 1.298 × 10 −15
2
γ Zn γ OH
2+ − (0.40)(0.76)2
Solubility = S = [Zn ] 2+
S (0.07)2 = 1.298 × 10 −15
 1.298 × 10 −15 
S = 2  = 2.6 × 10 M
−13
 (0.07) 
(d) the solution that results when you mix 20.0 mL of 0.100 M KOH with 80.0 mL of
0.0250 M ZnCl2 .
0.100 mmol
amount KOH = × 20.0 mL = 2.0 mmol
mL
0.0250 mmol
amount ZnCl2 = × 80.0 mL = 2.0 mmol
mL
2 mmol
[K + ] = = 0.02 M
100.0 mL
[OH− ] = 0
2 × 2.0 mmol
[Cl− ] = = 0.04 M
100.0 mL
7
1
2 mmol − (2 mmol)
2+
[Zn ] = 2 = 0.01 M
100.0 mL
1
μ=
2
(
0.02 × 12 + 0.040 × 12 + 0.01× 22 = 0.05 )
From Table 10-2,
γ Zn2+ = 0.48 γ OH− = 0.81
K sp 2
′ = aZn2+ aOH− = γ
Zn2+
[Zn2+ ] × γ OH
2 − 2
− [OH ]
3.0 × 10 −16 3.0 × 10 −16

[Zn2+ ][OH− ]2 = = = 9.53 × 10−16
γ Zn γ OH
2+
2
− (0.48)(0.81) 2
Solubility = S = [OH ] / 2 −
(0.01)[OH− ]2 = 9.53 × 10−16

1
 9.53 × 10−16  2
[OH ] = 
−
 = 3.09 × 10 M
−7
 0.01 
( )
S = 3.09 × 10 −7 M /2 = 1.5 × 10 −7 M
*8-14. Calculate the solubilities of the following compounds in a 0.0275 M solution of

Mg ( ClO4 )2 using (1) activities and (2) molar concentrations:
Solutions:
(a) AgSCN.
μ = ½[0.0275 × 22 + 2 × 0.0275 × 12] = 0.0825 Cannot use data in Table 8-2. Use
Equation 8-5
AgSCN(s)  Ag+ + SCN−
(1) For Ag+, γ Ag+ = 0.761; for SCN−, γ SCN − = 0.776
K sp = γ Ag+ [Ag + ]γ SCN− [SCN− ] = 1.1× 10 −12

1.1× 10 −12
[Ag + ][SCN− ] = = 1.86 × 10 −12
0.761× 0.776
S = [Ag+] = [SCN−]
S = 1.86 × 10−12 = 1.4 × 10−6 M
(2) S = 1.1× 10−12 = 1.0 × 10−6 M
8
(b) PbI2 .
PbI2 (s)  Pb2+ + 2I−

(1) γ Pb2+ = 0.388 γ I− = 0.769 K sp
′ = aPb2+ aI2− = γ Pb2+ [Pb2+ ] × (γ I− [I− ])2
7.9 × 10 −9 7.9 × 10 −9
[Pb2+ ][I− ]2 = = = 3.44 × 10−8
γ Pb γ I
2+ −
2
(0.388)(0.769)2
1 −
Solubility = S = [Pb2 + ] = [I ]
2
S (2S )2 = 3.44 × 10 −8
1
 3.44 ×10−8  3
S =  = 2.0 × 10 M
−3
 4 
1
 7.9 × 10−9  3
(2) S =  = 1.3 × 10 M
−3
 4 
(c) BaSO 4 .
BaSO4(s)  Ba2+ + SO42−

γ Ba = 0.40; γ SO
2+ 2− = 0.376
4
1.1× 10 −10 1.1× 10−10

[Ba2 + ][SO4 2 − ] = = = 7.3 × 10 −10
γ Ba γ SO2+ 2− (0.40)(0.376)
4
Solubility = S = [Ba ] = [SO4 2 − ]

2+
S 2 = 7.3 × 10 −10
S = 7.3 × 10 −10 = 2.7 × 10 −5 M
(2) S = 1.1 × 10−10 = 1.0 × 10−5 M
(d) Cd2Fe ( CN)6 .
Cd2Fe(CN)6 (s)  2Cd2+ + Fe(CN)6 4−

K sp = 3.2 × 10−17
Cd2Fe(CN)6(s)  2Cd2+ + Fe(CN)64−

(1) γ Cd2+ = 0.40 γ Fe(CN) 4− = 0.020
6
3.2 × 10−17 3.2 × 10 −17

[Cd2+ ]2 [Fe(CN)6 4 − ] = 2
= = 1.00 × 10−14
γ Cd γ Fe(CN)
2+ 4− (0.40)2 (0.020)
6
9
1
Solubility = S = [Cd2 + ] = [Fe(CN)6 4 − ]
2
(2S )2 S = 1.00 × 10 −14
1
 1.00 × 10 −14  3
S =  = 1.4 × 10 M
−5
 4 
1
 3.2 × 10 −17  3
(2) S =  = 2.0 × 10 M
−6
 4 
*8-15. Calculate the solubilities of the following compounds in a 0.0167 M solution of Ba (NO3 )2
using (1) activities and (2) molar concentrations:
Solutions:
(a) AgIO3 .
μ = ½[0.0167 × 22 + 2 × 0.0167 × 12] = 0.050

AgIO3(s)  Ag+ + IO3−
(1) γ Ag+ = 0.80 γ IO − = 0.82
3
3.1× 10 −8 3.1× 10 −8
[Ag + ][IO3 − ] = = = 4.7 × 10 −8
γ Ag γ IO
+ − (0.80)(0.82)
3
Solubility = S = [Ag + ] = [IO3 − ]

S 2 = 4.7 × 10 −8
S = 4.7 × 10−8 = 2.2 × 10 −4 M
(2) S = 3.1× 10−8 = 1.8 × 10 −4 M
(b) Mg ( OH)2 .
Mg(OH)2(s)  Mg2+ + 2OH−

(1) γ Mg2+ = 0.52 γ OH− = 0.81
7.1× 10−12 7.1× 10−12

[Mg2 + ][OH− ]2 = 2
= = 2.081× 10 −11
γ Mg γ OH2+ − (0.52)(0.81)2
1
Solubility = S = [Mg2 + ] = [OH− ]
2
S (2S )2 = 2.081× 10 −11
1
 2.081× 10−11  3
S =  = 1.7 × 10 M
−4
 4 
1
 7.1× 10−12  3
(2) S =  = 1.2 × 10 M
−4
 4 
10
(c) BaSO 4 .
BaSO4(s)  Ba2+ + SO42−
(1) γ Ba2+ = 0.46 γ SO 2− = 0.44

4
1.1× 10 −10 1.1× 10−10

[Ba2+ ][SO4 2− ] = = = 5.435 × 10 −10
γ Ba γ SO
2+ 2− (0.46)(0.44)
4
Solubility = S = [SO4 ] 2−
(0.0167) × S = 5.435 × 10−10

 5.435 × 10 −10 
S =  = 3.3 × 10 M
−8
 0.0167 
 1.1× 10−10 
(2) S =   = 6.6 × 10 M
−9
 0.0167 
(d) La (IO3 )3 .
La(IO3)3(s)  La3+ + 3IO3

3
(1) γ La3+ = 0.24 γ IO = 0.82
− K sp = aLa3+ aIO − = γ
La3+
[La3+ ] × (γ IO − [IO3 − ])3
3 3 3
1.0 × 10−11 1.0 × 10−11

[La3+ ][IO3 − ]3 = = = 7.557 × 10 −11
γ La γ IO3
3+ − (0.24)(0.82)3
3
1
Solubility = S = [La3 + ] = [IO3 − ]
3
S (3S )3 = 7.557 × 10−11

1
 7.557 × 10 −11  4
S =  = 1.3 × 10 M
−3
 27 
1
 1.0 × 10 −11  4
(2) S =  = 7.8 × 10 M
−4
 27 
8-16. Calculate the % relative error in solubility by using concentrations instead of activities for
the following compounds in 0.0350 M KNO3 using the thermodynamic solubility
products listed in Appendix 2.
Solutions:
*(a) CuCl (αCu+ = 0.3 nm)
CuCl(s)  Cu+ + Cl−
11
Since Cu+ has an effective diameter of 0.3, then

(1) γ Cu+ = 0.83 γ Cl− = 0.83 ′ = aCu+ aCl− = γ Cu+ [Cu+ ] × γ Cl− [Cl− ]
K sp
1.9 × 10−7 1.9 × 10−7
[Cu+ ][Cl− ] = = = 2.758 × 10−7
γ Cu γ Cl
+ − (0.83)(0.83)
Solubility = S = [Cu ] = [Cl− ]
+
S 2 = 2.758 × 10−7
S = 2.758 × 10−7 = 5.25 × 10−4 M
(2) S = 1.9 × 10−7 = 4.4 × 10−4 M
relative error =
( 4.4 × 10 −4
− 5.25 × 10−4 ) × 100% = −16%
−4
5.25 × 10
(b) Fe ( OH)2
Fe(OH)2(s)  Fe2+ + 2OH−
(1) γ Fe2+ = 0.53 γ OH− = 0.83 2

′ = aFe2+ aOH
K sp − = γ
Fe2+
[Fe2+ ] × (γ OH− [OH− ])2
4.1× 10−15 4.1× 10−15
[Fe2+ ][OH− ]2 = = = 1.123 × 10−14
2
γ Fe γ OH
2+ − (0.53)(0.83)2
1
Solubility = S = [Fe2 + ] = [OH− ]
2
S (2S )2 = 1.123 × 10 −14
1
 1.123 × 10−14  3
S = −5
 = 1.4 × 10 M
 4 
1
 4.1 × 10−15  3
(2) S =  −5
 = 1.0 × 10 M
 4 
1.0 × 10−5 − 1.4 × 10−5
relative error = × 100% = −29%
1.4 × 10−5
*(c) Fe ( OH)3
Fe(OH)3  Fe3+ + 3OH−
(1) γ Fe3+ = 0.281 γ OH− = 0.835 3

′ = aFe3+ aOH
K sp − = γ
Fe3+
[Fe3+ ] × (γ OH− [OH− ])3
2 × 10 −39 2 × 10−39
[Fe3+ ][OH− ]3 = 3
= = 1.223 × 10 −38 retaining figures until the end
γ Fe γ OH
3+ − (0.281)(0.835)3
1
Solubility = S = [Fe3 + ] = [OH− ]
3
S (3S )3 = 1.223 × 10 −38
12
1
 1.223 × 10−38 4
S =  = 1.46 × 10 M
−10
 27
 
1
 2 × 10−39  4
(2) S =   = 9.3 × 10 M
−11
 27 
9.3 × 10 −11 − 1.46 × 10 −10
1.46 × 10−10
(d) La (IO3 )3
La(IO3)3(s)  La3+ + 3IO3
(1) γ La3+ = 0.281 γ IO − = 0.835 3

′ = aLa3+ aIO
K sp − = γ
La3+
[La3+ ] × (γ IO − [IO3 − ])3
3 3 3
1.0 × 10 −11 1.0 × 10−11

[La ][IO3 ] =
3+ − 3
= = 6.113 × 10−11
γ La γ IO3
3+ − (0.281)(0.835) 3
3
1
Solubility = S = [La3 + ] = [IO3 − ]
3
S (3S ) = 6.113 × 10
3 −11
1
 6.113 × 10−11  4
S = −3
 = 1.2 × 10 M
 27 
1
 1.1× 10 −11  4
(2) S =   = 8.0 × 10 M
−4
 27 
8.0 × 10 −4 − 1.2 × 10−3
1.2 × 10 −3
*(e) Ag3 AsO4 (α AsO43− = 0.4 nm)
Ag3(AsO4)(s)  3Ag+ + AsO43−

(1) γ Ag+ = 0.827 γ AsO 3− = 0.205 K sp 3
′ = aAg + a
AsO 3−
= (γ Ag+ [Ag+ ])3 × γ AsO 3− [AsO4 3 − ]
4 4 4
6 × 10 −23 6 × 10 −23
[Ag + ]3 [AsO4 3 − ] = = = 5.17 × 10 −22
3
γ Ag γ AsO
+ 3− (0.827)3 (0.205)
4
1
Solubility = S = [AsO3 4 − ] = [Ag + ]
3
(3S )3 S = 5.17 × 10 −22
1
 5.17 × 10−22  4
S =  = 2.1× 10 M
−6
 27 
1
 6 × 10−23  4
(2) S =   = 1.2 × 10 M
−6
 27 
1.2 × 10 −6 − 2.1 × 10 −6
2.1× 10−6
13
8-17. Calculate the % relative error in hydronium ion concentration by using concentrations
instead of activities in calculating the pH of the following buffer solutions using the
thermodynamic constants found in Appendix 3.
Solution:
*(a) 0.175 M HOAc and 0.275 M NaOAc
In this buffer solution, we assume [HOAc] = cHOAc and [OAC−] = cNaOAc. We also
assume that the ionic strength is contributed solely by NaOAc, neglecting H3O+ and
OH−.
μ = ½[0.275 × 12 + 0.275 × 12] = 0.275
(0.51)(1)2 0.275
− log γ H O+ = = 0.1046 γ H O+ = 0.786
3
1 + (3.3)(0.9) 0.275 3
(0.51)(1)2 0.275
− log γ OAc− = = 0.1541 γ OAc− = 0.701
1 + (3.3)(0.425) 0.275
γ H O+ [H3O+ ]γ OAc− [OAc − ]
Ka = 3
[HOAc]
[H3O+ ][OAc − ] Ka 1.75 × 10 −5
K a′ = = = = 3.176 × 10 −5
[HOAc] γ H O γ OAc
+ − 0.786 × 0.701
3
K a′ [HOAc] 3.176 × 10 −5 × 0.175

[H3O+ ] = = = 2.0 × 10−5 M
[OAc ] −
0.275
pH = 4.69
With no activity corrections
1.75 × 10 −5 × 0.175
[H3O+ ] = = 1.1× 10 −5 M
0.275
pH = 4.96
1.1× 10 −5 − 2.0 × 10 −5
relative error in [H3O+ ] = × 100% = −45%
2.0 × 10−5
(b) 0.0500 M NH3 and 0.100 M NH4 Cl
In this buffer, we assume that the ionic strength is contributed by only NH4Cl and
that cNH = [NH3 ] and cNH + = [NH4 + ].
3 4
NH3 + H2O  NH4+ + OH− Kb = Kw/Ka = 1.00 × 1014/5.70 × 10−10 = 1.75 × 10−5
μ = ½[0.100 × 12 + 0.100 × 12] = 0.100
14
From Table 8-2, γ NH + = 0.75, γ OH− = 0.76

4
aNH + aOH− [NH4 + ][OH− ]γ NH + γ OH−

Kb = 4
= 4
= K b′ γ NH + γ OH−
aNH [NH3 ] 4
3
[NH4 + ][OH− ] Kb 1.75 × 10 −5

K b′ = = = = 3.07 × 10 −5
[NH3 ] γ NH + γ OH− 0.75 × 0.76
4
K b′ [NH3 ]
3.07 × 10 −5 × 0.050
[OH− ] = = = 1.5 × 10 −5 M
[NH4 + ] 0.100
Kw
1.00 × 10 −14
[H3O+ ] = −5
== 6.7 × 10 −10 M
[OH ] 1.5 × 10
−
Assuming activity coefficients are unity,

K b [NH3 ] 1.75 × 10 −5 × 0.050
[OH− ] = = = 8.8 × 10 −6 M
[NH4 ] +
0.100
Kw
1.00 × 10 −14
[H3O+ ] = = = 1.1× 10 −9 M
[OH− ] 8.8 × 10 −6
1.1× 10 −9 − 6.7 × 10 −10
relative error = = 64%
6.7 × 10 −10
(c) 0.0200 M ClCH2COOH and 0.0500 M ClCH2COONa (aClCH2COO− = 0.35)
ClHOAc + H2O  H3O+ + ClOAc− Ka = 1.36 × 103

We assume that the ionic strength is created by NaCl, [HOAc] = 0.050, [ClHOAc] =
0.020 M, and [ClOAc−] = 0.050 M
Hence, γ H O+ = 0.85, γ ClOAc− = 0.81
3
[H3O ][ClOAc− ]
+
Ka 1.36 × 10 −3
K a′ = = = = 1.975 × 10−3
[ClHOAc] γ H O γ ClOAc
+ − 0.85 × 0.81
3
1.975 × 10−3 × [ClHOAc] 1.975 × 10−3 × 0.020

[H3O+ ] = = = 7.9 × 10−4 M
[ClOAc ]−
0.050
With no activity corrections,
1.36 × 10−3 × 0.020
[H3O+ ] = = 5.4 × 10−4 M
0.050
5.4 × 10−4 − 7.9 × 10−4
relative error = × 100% = 31.6%
7.9 × 10 −4
8-18. Design and construct a spreadsheet to calculate activity coefficients in a format similar to
Table 8-2. Enter values of aX in cells A3, A4, A5, and so forth, and enter ionic charges in
cells B3, B4, B5, and so forth. Enter in cells C2:G2 the same set of values for ionic
strength listed in Table 8-2. Enter the formula for the activity coefficients in cells C3:G3.
Be sure to use absolute cell references for ionic strength in your formulas for the activity
coefficients. Finally, copy the formulas for the activity coefficients into the rows below
row C by highlighting C3:G3 and dragging the fill handle downward. Compare the activity
15
coefficients that you calculate to those in Table 8-2. Do you find any discrepancies? If so,
explain how they arise.
Solution:
See spreadsheet.
16

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Solution and Answer Guide

(b) thermodynamic and concentration equilibrium constants.

8-2. List several general properties of activity coefficients.

Activity coefficients have the following properties:

MgCl2 + 2NaOH  Mg(OH)2 (s) + 2NaCl

(b) hydrochloric acid?

HCl + NaOH  H2O + NaCl

(c) acetic acid?

HOAc + NaOH  H2O + NaOAc

3NaOH + FeCl3  Fe(OH)3 (s) + 3NaCl

3AgNO3 + FeCl3  Fe(NO3 )3 + 3AgCl(s)

8-9. Calculate the ionic strength of a solution that is

μ = ½[0.025 × 22 + 0.025 × 22] = 0.10

(b) 0.25 M in (NH4 )2 CrO4 .

μ = ½[0.50 × 12 + 0.25 × 22] = 0.75

*(c) 0.25 M in FeCl3 and 0.15 M in FeCl2 .

μ = ½[0.25 × 32 + 0.75 × 12 + 0.15 × 22 + 0.30 × 12] = 1.95

(d) 0.025 M in La (NO3 )3 and 0.050 M in Fe (NO3 )2 .

μ = ½[0.025 × 32 + 0.075 × 12 + 0.05 × 22 + 0.10 × 12] = 0.30

8-10. Use Equation 8-5 to calculate the activity coefficient of

Rounding these results, gives for the γ X

(b) Pb21 at μ = 0.026.

*(c) Ce41 at μ = 0.065.

(d) Sn41 at μ = 0.040.

(b) μ = 0.01 γ Pb = 0.665 μ = 0.05 γ Pb = 0.45

(c) μ = 0.05 γ Ce = 0.10 μ = 0.10 γ Ce = 0.063

(d) μ = 0.01 γ Sn = 0.252 μ = 0.05 γ Sn = 0.10

8-12. For a solution in which μ = 6.5 × 10−2 , calculate K sp

For La3+, γ La3+ = 0.2158. For IO3−, γ IO − = 0.7935

For Mg2+, γ = 0.4888; for NH4+, γ = 0.7809; for PO43−, γ = 0.1332

*8-13. Use activities to calculate the molar solubility of Zn ( OH)2 in

Zn(OH)2(s)  Zn2+ + 2OH− Ksp = 3.0 × 10−16

3.0 × 10 −16 3.0 × 10 −16

Solubility = S = [Zn2+] = ½[OH−]

(b) 0.0250 M K 2 SO4 .

μ = ½[2 × 0.0250 × 12 + 0.0250 × 22] = 0.15/2 = 0.075

Solubility = S = [Zn2+] = ½[OH−]

3.0 × 10 −16 3.0 × 10 −16

3.0 × 10 −16 3.0 × 10 −16

(0.01)[OH− ]2 = 9.53 × 10−16

*8-14. Calculate the solubilities of the following compounds in a 0.0275 M solution of

(1) For Ag+, γ Ag+ = 0.761; for SCN−, γ SCN − = 0.776

K sp = γ Ag+ [Ag + ]γ SCN− [SCN− ] = 1.1× 10 −12

S = 1.86 × 10−12 = 1.4 × 10−6 M

(2) S = 1.1× 10−12 = 1.0 × 10−6 M

PbI2 (s)  Pb2+ + 2I−

BaSO4(s)  Ba2+ + SO42−

1.1× 10 −10 1.1× 10−10

Solubility = S = [Ba ] = [SO4 2 − ]

(d) Cd2Fe ( CN)6 .

Cd2Fe(CN)6 (s)  2Cd2+ + Fe(CN)6 4−

Cd2Fe(CN)6(s)  2Cd2+ + Fe(CN)64−

3.2 × 10−17 3.2 × 10 −17

μ = ½[0.0167 × 22 + 2 × 0.0167 × 12] = 0.050

Solubility = S = [Ag + ] = [IO3 − ]

Mg(OH)2(s)  Mg2+ + 2OH−

7.1× 10−12 7.1× 10−12

BaSO4(s)  Ba2+ + SO42−

(1) γ Ba2+ = 0.46 γ SO 2− = 0.44

1.1× 10 −10 1.1× 10−10