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Activity Coefficients in Solutions

This chapter discusses fundamentals of analytical chemistry including activity, activity coefficients, ionic strength, and their relationships. It provides definitions and properties, then gives examples of how changing conditions impacts these concepts. There are also example calculations and problems throughout the chapter.

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Christine Tenorio
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58 views20 pages

Activity Coefficients in Solutions

This chapter discusses fundamentals of analytical chemistry including activity, activity coefficients, ionic strength, and their relationships. It provides definitions and properties, then gives examples of how changing conditions impacts these concepts. There are also example calculations and problems throughout the chapter.

Uploaded by

Christine Tenorio
Copyright
© All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as DOC, PDF, TXT or read online on Scribd

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, A, is the numerical factor necessary to convert the molar

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

aA=A[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)

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)

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)

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)

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

strength is unchanged.

(c)

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)

(b)

(c)

(d)

10-8

Z   -log  
(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)

(b)

(c)
Fundamentals of Analytical Chemistry: 8th ed. Chapter 10

(d)

10-10 (a)

(b)

(c)

(d)

10-11

(a)
Fundamentals of Analytical Chemistry: 8th ed. Chapter 10

(b)
Fundamentals of Analytical Chemistry: 8th ed. Chapter 10

(c)

(d)
Fundamentals of Analytical Chemistry: 8th ed. Chapter 10

10-12

(a)

(b)
Fundamentals of Analytical Chemistry: 8th ed. Chapter 10

(c)
Fundamentals of Analytical Chemistry: 8th ed. Chapter 10

(d)

10-13

(a)
Fundamentals of Analytical Chemistry: 8th ed. Chapter 10

(b)

(c)
Fundamentals of Analytical Chemistry: 8th ed. Chapter 10

(d)

10-14

(a)

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

(b)
Fundamentals of Analytical Chemistry: 8th ed. Chapter 10

(c)

(d)
Fundamentals of Analytical Chemistry: 8th ed. Chapter 10

(e)

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

then
Fundamentals of Analytical Chemistry: 8th ed. Chapter 10

10-15 (a)

(b)

(c)
Fundamentals of Analytical Chemistry: 8th ed. Chapter 10
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
6 c(Ba(NO3)2) pc(Ba(NO3)2) s(conc) ps(conc) s(act) ps(act)  (Ag+) (IO3-)
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
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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
6 c(Ba(NO3)2) pc(Ba(NO3)2) s(conc) ps(conc) s(act) ps(act)  (Mg2+) (OH-)
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
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31
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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)))
A B C D E F G H I
1 Problem 10-16(c)
2
3 Ksp(BaSO4)
Fundamentals of Analytical Chemistry: 8th ed. Chapter 10

4 1.10E-10
5
6 c(Ba(NO3)2) pc(Ba(NO3)2) s(conc) ps(conc) s(act) ps(act)  (Ba2+) (SO42-)
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
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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)))

A B C D E F G H I
1 Problem 10-16(d)
2
3 Ksp(La(IO3)3
4 1.00E-11
Fundamentals of Analytical Chemistry: 8th ed. Chapter 10

5
6 c(Ba(NO3)2) pc(Ba(NO3)2) s(conc) ps(conc) s(act) ps(act)  (La3+) (IO3-)
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
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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)))

10-17

A B C D E F G
1 Problem 10-17
2
Fundamentals of Analytical Chemistry: 8th ed. Chapter 10

3 
4 x 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)))

Common questions

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Ionic strength alterations can significantly affect the solubility product constant (Ksp) by influencing the activity coefficients of the involved ions. For example, as ionic strength increases, the activity coefficients of ions like Ag+ and IO3- in the salt AgIO3 decrease. This change in activity coefficients alters the effective concentrations of the ions, thus modifying the apparent solubility of the salt .

In a BaSO4 system, increasing concentrations of Ba(NO3)2 lead to a decrease in the activity coefficients of both Ba2+ and SO4 2-. Higher concentrations result in increased ionic strength, which typically reduces activity coefficients for multivalent ions due to enhanced electrostatic interactions among ions, altering the solubility equilibrium of BaSO4 due to changes in effective ionic activities .

The activity coefficient is influenced by the ionic strength of the solution, with it approaching unity in very dilute solutions. For a given ionic strength, the activity coefficient becomes smaller as the charge of the chemical species increases. Therefore, ions with higher charges exhibit greater deviations from ideality as compared to singly-charged ions. Additionally, at any ionic strength, the activity coefficients are approximately equal for chemical species with the same charge state .

The non-charged nature of NH3 means that its activity coefficient is unity. This is because non-ionic species are not affected by electrostatic interactions that typically decrease the activity coefficient of charged ions as ionic strength increases .

The initial slope of the change in activity coefficient for Ca2+ is steeper than that for K+ because the deviations from ideality are more pronounced for ions with higher charges (multivalent). For Ca2+, being a doubly-charged ion, the activity coefficient deviates more sharply from unity in comparison to the singly-charged K+ ion .

Adding FeCl3 to HCl or a solution containing Ag+ affects ionic strength differently depending on the ions involved. Adding FeCl3 to HCl increases the ionic strength due to the introduction of additional ions. In contrast, in a solution with Ag+, replacing the univalent Ag+ with the trivalent Fe3+ increases the ionic strength more significantly due to the greater charge of Fe3+, which affects the ionic strength by a charge-squared factor .

Replacing divalent ions such as Mg2+ with univalent ions like Na+ increases the activity coefficient, indicating a decrease in ionic strength. This occurs because the ionic strength of a solution is partly determined by the squared charges of the ions present, and replacing a divalent ion with a univalent one reduces the overall ionic contribution from that species .

Adding NaOH to HCl, a strong acid, keeps the activity coefficient relatively constant since there is no change in the ionic charges in the equilibria, maintaining the ionic strength unchanged. Conversely, adding NaOH to acetic acid, a weak acid, results in the formation of Na+ and the conjugate base OAc-, leading to an increase in ionic strength and a decrease in the activity coefficient due to the creation of new ions .

The thermodynamic equilibrium constant pertains to an ideal system where each species is unaffected by others, remaining numerically constant and independent of ionic strength. In contrast, the concentration equilibrium constant is influenced by the molar concentrations of reactants, products, and other solute species, thus being dependent on changes in ionic strength and interactions among species in the solution .

Assuming an effective ion diameter is critical for calculating activity coefficients as it affects the estimation of how ions distribute in a solution. For Cu+, assuming an effective diameter similar to other cations informs the calculations for how closely ions pack together, impacting the electrostatic interactions and resulting activity coefficients. Similarly, for AsO4 3-, an assumed effective diameter provides a basis for determining the ion's influence on its surrounding ionic environment and activity coefficient .

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