Activity and the Systematic

8 Treatment of Equilibrium

HYDRATED IONS

Estimated Number of Waters

of Hydration* Li+ Be2+ Fe2+ CO32– F–

Molecule Tightly bound H2O Ionic

radius
CH3CH2CH3 0
C6H6 0
CH3CH2Cl 0
Hydrated
CH3CH2SH 0 radius
Na+ Mg2+ Fe3+ SO42– Cl–
CH3 ßOßCH3 1
CH3CH2OH 1
(CH3 ) 2C¢O 1.5
CH3CH¢O 1.5
CH3CO2H 2
CH3CΩN 3
O K+ Ca2+ NO–3 CIO4– Br –

CH3CNHCH3 4
CH3NO2 5
CH3CO2 5
CH3NH2 6
CH3SO3H 7
NH3 9 Rb+ Sr2+ NH4+ IO3– I–
CH3SO3 10
500 pm
NH4 12
*From S. Fu and C. A. Lucy, “Prediction of Ionic and hydrated radii of several ions. Smaller, more highly charged ions bind water molecules more
Electrophoretic Mobilities,” Anal. Chem. 1998, 70, 173. tightly and behave as larger hydrated species.3

Ions and molecules in solution are surrounded by an organized sheath of solvent molecules.
The oxygen atom of H2O has a partial negative charge and each hydrogen atom has half as
much positive charge.

δ
H H 200 pm 220 pm
Cl
O 2δ O Li H O
330 pm H
H H
δ

Water binds to cations through the oxygen atom. The first coordination sphere of Li, for
example, is composed of ⬃4 H2O molecules.1 Cl binds ⬃6 H2O molecules through hydro-
gen atoms.1,2 H2O exchanges rapidly between bulk solvent and ion-coordination sites.
Ionic radii in the figure are measured by X-ray diffraction of ions in crystals. Hydrated
radii are estimated from diffusion coefficients of ions in solution and from the mobilities of
aqueous ions in an electric field.3,4 Smaller, more highly charged ions bind more water mol-
ecules and behave as larger species in solution. The activity of aqueous ions, which we
study in this chapter, is related to the size of the hydrated species.

140 CHAPTER 8 Activity and the Systematic Treatment of Equilibrium

In Chapter 6, we wrote the equilibrium constant for a reaction in the form 300

[FeSCN2+] / [Fe3+][SCN – ]
[Fe(SCN) 2]
Fe3  SCN T Fe(SCN) 2 K (8-1) 250
[Fe3][SCN]
Pale yellow Colorless Red 200

Figure 8-1, Demonstration 8-1, and Color Plate 3 show that the concentration quotient in
150
Equation 8-1 decreases if you add the “inert” salt KNO3 to the solution. That is, the equilib-
rium “constant” is not really constant. This chapter explains why concentrations are replaced
100
by activities in the equilibrium constant and how activities are used. 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
KNO3 added (M)

8-1 The Effect of Ionic Strength Figure 8-1 Student data showing that the

on Solubility of Salts equilibrium quotient of concentrations for the

reaction Fe3  SCN T Fe(SCN)2 decreases
Consider a saturated solution of CaSO4 in distilled water. as potassium nitrate is added to the solution.
Color Plate 3 shows the fading of the red color
CaSO4 (s) T Ca2  SO2
4 Ksp  2.4 105 (8-2) of Fe(SCN)2 after KNO3 has been added.
Problem 13-11 gives more information on this
Figure 6-1 showed that the solubility is 0.015 M. The dissolved species are mainly 0.010 M chemical system. [From R. J. Stolzberg, “Discovering
Ca2, 0.010 M SO2 4 , and 0.005 M CaSO4 (aq) (an ion pair). a Change in Equilibrium Constant with Change in
Now an interesting effect is observed when a salt such as KNO3 is added to the solution. Ionic Strength,” J. Chem. Ed. 1999, 76, 640.]
Neither K nor NO 3 reacts with either Ca
2 or SO2. Yet, when 0.050 M KNO is added to
4 3
the saturated solution of CaSO4, more solid dissolves until the concentrations of Ca2 and
SO2
4 have each increased by about 30%.
In general, adding an “inert” salt (KNO3 ) to a sparingly soluble salt (CaSO4 ) increases Addition of an “inert” salt increases the
the solubility of the sparingly soluble salt. By “inert,” we mean a salt whose ions do not react solubility of an ionic compound.
with the other ions. When we add salt to a solution, we say that the ionic strength of the solu-
tion increases. The definition of ionic strength will be given shortly.

The Explanation
Why does the solubility increase when salts are added to the solution? Consider one particu- Ionic atmospheres
lar Ca2 ion and one particular SO2 2
4 ion in the solution. The SO4 ion is surrounded by
cations (K, Ca2) and anions (NO 3 , SO2) in the solution. However, for the average anion,
4
δ– δ+
there will be more cations than anions near it because cations are attracted to the anion, but
anions are repelled. These interactions create a region of net positive charge around any par- + –
ticular anion. We call this region the ionic atmosphere (Figure 8-2). Ions continually diffuse
into and out of the ionic atmosphere. The net charge in the atmosphere, averaged over time,
is less than the charge of the anion at the center. Similarly, an atmosphere of negative charge
surrounds any cation in solution. Cation Anion
The ionic atmosphere attenuates (decreases) the attraction between ions. The cation plus its
negative atmosphere has less positive charge than the cation alone. The anion plus its ionic Figure 8-2 An ionic atmosphere, shown as
atmosphere has less negative charge than the anion alone. The net attraction between the cation a spherical cloud of charge d or d,
surrounds ions in solution. The charge of the
with its ionic atmosphere and the anion with its ionic atmosphere is smaller than it would be
atmosphere is less than the charge of the
between pure cation and anion in the absence of ionic atmospheres. The greater the ionic central ion. The greater the ionic strength of
strength of a solution, the higher the charge in the ionic atmosphere. Each ion-plus-atmosphere the solution, the greater the charge in each
contains less net charge and there is less attraction between any particular cation and anion. ionic atmosphere.

Demonstration 8-1 Effect of Ionic Strength on Ion Dissociation5

This experiment demonstrates the effect of ionic strength on the To demonstrate the effect of ionic strength on the dissociation
dissociation of the red iron(III) thiocyanate complex: reaction, mix 300 mL of 1 mM FeCl3 with 300 mL of 1.5 mM
NH4SCN or KSCN. Divide the pale red solution into two equal
Fe(SCN) 2 T Fe3  SCN
portions and add 12 g of KNO3 to one of them to increase the
Red Pale yellow Colorless
ionic strength to 0.4 M. As KNO3 dissolves, the red Fe(SCN) 2
Prepare a solution of 1 mM FeCl3 by dissolving 0.27 g of complex dissociates and the color fades (Color Plate 3).
FeCl3
6H2O in 1 L of water containing 3 drops of 15 M (con- Addition of a few crystals of NH4SCN or KSCN to either
centrated) HNO3. The acid slows the precipitation of Fe(OH) 3, solution drives the reaction toward formation of Fe(SCN) 2,
which occurs in a few days and necessitates the preparation of thereby intensifying the red color. This reaction demonstrates
fresh solution for this demonstration. Le Châtelier’s principle—adding a product creates more reactant.

8-1 The Effect of Ionic Strength on Solubility of Salts 141

 Increasing ionic strength therefore reduces the attraction between any particular Ca2
Potassium hydrogen tartrate solubility (M)
ion and any SO2 4 ion, relative to their attraction for each other in distilled water. The effect

0.05
is to reduce their tendency to come together, thereby increasing the solubility of CaSO4.
MgSO4 Increasing ionic strength promotes dissociation into ions. Thus, each of the following
0.04 reactions is driven to the right if the ionic strength is raised from, say, 0.01 to 0.1 M:
NaCl
0.03
Glucose Fe(SCN) 2 T Fe3  SCN
0.02 Thiocyanate

0.01
KCl OH T—— O –H
0.00 Phenol Phenolate
0.00 0.02 0.04 0.06 0.08 0.10
Concentration of added HO OH HO OH
substance (M)
å å å å
HO2CCHCHCO2K(s)—T—HO2CCHCHCO2 ––K
Figure 8-3 Solubility of potassium hydrogen
tartrate increases when the salts MgSO4
Potassium hydrogen tartrate
or NaCl are added. There is no effect when the
Figure 8-3 shows the effect of added salt on the solubility of potassium hydrogen tartrate.
neutral compound glucose is added. Addition
of KCl decreases the solubility. (Why?) [From
C. J. Marzzacco, “Effect of Salts and Nonelectrolytes
on the Solubility of Potassium Bitartrate,” J. Chem. Ed.
What Do We Mean by “Ionic Strength”?
1998, 75,1628.] Ionic strength, , is a measure of the total concentration of ions in solution. The more
highly charged an ion, the more it is counted.

1 1
Ionic strength:  (c z2  c2 z22  p )  a ci z2i (8-3)
2 11 2 i

where ci is the concentration of the ith species and zi is its charge. The sum extends over all
ions in solution.

Example Calculation of Ionic Strength

Find the ionic strength of (a) 0.10 M NaNO3; (b) 0.010 M Na2SO4; and
(c) 0.020 M KBr plus 0.010 M Na2SO4.

Solution

5[Na]
(1) 2  [NO

3 ]
(1) 6
1
(a)  2
2

50.10
1  0.10
16  0.10 M

1

2

5[Na]
(1) 2  [SO2

4 ]
(2) 6
1
(b)  2
2

5 (0.020
1)  (0.010
4)6  0.030 M

1

2
Note that [Na]  0.020 M because there are two moles of Na per mole of Na2SO4.

5[K]
(1) 2  [Br]
(1) 2  [Na]
(1) 2  [SO2

4 ]
(2) 6
1
(c)  2
2

5 (0.020
1)  (0.020
1)  (0.020
1)  (0.010
4)6  0.050 M

1

2

Ionic NaNO3 is called a 1:1 electrolyte because the cation and the anion both have a charge of 1.
Electrolyte Molarity strength For 1:1 electrolytes, the ionic strength equals the molarity. For other stoichiometries (such as
1:1 M M the 2:1 electrolyte Na2SO4), the ionic strength is greater than the molarity.
2:1 M 3M Computing the ionic strength of any but the most dilute solutions is complicated because
3:1 M 6M salts with ions of charge 2 are not fully dissociated. In Box 8-1 we find that, at a formal
2:2 M 4M concentration of 0.025 M MgSO4, 35% of Mg2 is bound in the ion pair, MgSO4 (aq) . The
higher the concentration and the higher the ionic charge, the more the ion pairing. There is no
simple way to find the ionic strength of 0.025 M MgSO4.

142 CHAPTER 8 Activity and the Systematic Treatment of Equilibrium

 Box 8-1 Salts with Ions of Charge  0 2 0 Do Not Fully Dissociate6

Salts composed of cations with a charge of 1 and anions with a Percentage of metal ion bound as ion
charge of 1 dissociate almost completely at concentrations pair in 0.025 F MxLy solutiona
6 0.1 M. Salts containing ions with a charge 2 are less dissoci- L
ated, even in dilute solution. Appendix J gives formation constants M Cl SO2
4

for ion pairing: Na 0.6% 4%

Ion pair formation Mg2 8% 35%
Mn (aq)  Lm (aq) T MnLm (aq)
constant: a. The size of ML was taken as 500 pm to compute its activity coefficient.
Ion pair
[ML]ML The table tells us that 0.025 F NaCl is only 0.6% associated as
K NaCl (aq) and Na2SO4 is 4% associated as NaSO 4 (aq) . For
[M]M[L]L
MgSO4, 35% is ion paired. A solution of 0.025 F MgSO4 contains
where the i are activity coefficients. With constants from Appen- 0.016 M Mg2, 0.016 M SO2 4 , and 0.009 M MgSO4 (aq). The
dix J, activity coefficients from Equation 8-6, craft, and persist- ionic strength of 0.025 F MgSO4 is not 0.10 M, but just 0.065 M.
ence, you might calculate the following percentages of ion pairing Problem 8-26 provides an example of the type of calculation in
in 0.025 F solutions: this box.

8-2 Activity Coefficients

The equilibrium constant expression in Equation 8-1 does not predict any effect of ionic
strength on a chemical reaction. To account for the effect of ionic strength, concentrations are
replaced by activities:

Activity of C: A C  [C]C (8-4)

c c a Activity coefficient
Activity Concentration of C
of C of C

The activity of species C is its concentration multiplied by its activity coefficient. The activ- Do not confuse the terms activity and activity
ity coefficient measures the deviation of behavior from ideality. If the activity coefficient coefficient.
were 1, then the behavior would be ideal and the form of the equilibrium constant in Equa-
tion 8-1 would be correct.
The correct form of the equilibrium constant is

General form of A cC A dD [C]ccC[D]ddD Equation 8-5 is the “real” equilibrium constant.

K  (8-5) Equation 6-2, the concentration quotient, Kc,
equilibrium constant: A AA B
a b [A]aaA[B]bbB
did not include activity coefficients:
[C]c[D]d
Equation 8-5 allows for the effect of ionic strength on a chemical equilibrium because the Kc  (6-2)
[A]a[B]b
activity coefficients depend on ionic strength.
For Reaction 8-2, the equilibrium constant is
Ksp  A Ca2A SO42  [Ca2]Ca2[SO2
4 ]SO42

If the concentrations of Ca2 and SO2 4 are to increase when a second salt is added to
increase ionic strength, the activity coefficients must decrease with increasing ionic strength.
At low ionic strength, activity coefficients approach unity, and the thermodynamic equi-
librium constant (8-5) approaches the “concentration” equilibrium constant (6-2). One way
to measure a thermodynamic equilibrium constant is to measure the concentration ratio (6-2)
at successively lower ionic strengths and extrapolate to zero ionic strength. Commonly, tabu-
lated equilibrium constants are not thermodynamic constants but just the concentration ratio
(6-2) measured under a particular set of conditions.

Example Exponents of Activity Coefficients

Write the solubility product expression for La2 (SO4 ) 3 with activity coefficients.

Solution Exponents of activity coefficients are the same as exponents of concentrations:

Ksp  A 2La3A 3SO 2
4
 [La3]22La3[SO2
4 ] SO42
3 3

8-2 Activity Coefficients 143

 Activity Coefficients of Ions
The ionic atmosphere model leads to the extended Debye-Hückel equation, relating activ-
ity coefficients to ionic strength:

Extended Debye- 0.51z2 1

Hückel equation: log   (at 25°C) (8-6)
1  (1 /305)

1 pm (picometer)  1012 m In Equation 8-6,  is the activity coefficient of an ion of charge z and size  (picometers, pm)
in an aqueous solution of ionic strength . The equation works fairly well for  0.1 M. To
find activity coefficients for ionic strengths above 0.1 M (up to molalities of 2–6 mol/kg for
many salts), more complicated Pitzer equations are usually used.7
Table 8-1 lists sizes () and activity coefficients of many ions. All ions of the same size
and charge appear in the same group and have the same activity coefficients. For example,
Ba2 and succinate ion [O2CCH2CH2CO 
2 , listed as (CH2CO2 ) 2] each have a size of 500 pm
and are listed among the charge  2 ions. At an ionic strength of 0.001 M, both of these
ions have an activity coefficient of 0.868.

Table 8-1 Activity coefficients for aqueous solutions at 25°C

Ion
Ionic strength (␮, M)
size
Ion (␣, pm) 0.001 0.005 0.01 0.05 0.1
Charge ⴝ ⴞ1
H 900 0.967 0.933 0.914 0.86 0.83
(C6H5)2CHCO 2 , (C3H7)4N
 800 0.966 0.931 0.912 0.85 0.82
(O2N)3C6H2O, (C3H7)3NH, CH3OC6H4CO 2 700 0.965 0.930 0.909 0.845 0.81
Li, C6H5CO  
2 , HOC6H4CO2 , ClC6H4CO2 , C6H5CH2CO2 ,

 
CH2£CHCH2CO2 , (CH3)2CHCH2CO2 , (CH3CH2)4N , (C3H7)2NH2  600 0.965 0.929 0.907 0.835 0.80
Cl2CHCO  
2 , Cl3CCO2 , (CH3CH2)3NH , (C3H7)NH3
 500 0.964 0.928 0.904 0.83 0.79
Na , CdCl , ClO2 , IO3 , HCO3 , H2PO4 , HSO3 , H2AsO
      
4,
Co(NH3)4(NO2)2, CH3CO 
2 , ClCH2CO2 , (CH3)4N ,


(CH3CH2)2NH2, H2NCH2CO 2 450 0.964 0.928 0.902 0.82 0.775

H NCH CO H, (CH ) NH, CH CH NH 400 0.964 0.927 0.901 0.815 0.77
3 2 2 3 3 3 2 3
OH, F, SCN, OCN, HS, ClO    
3 , ClO4 , BrO3 , IO4 , MnO4 ,
  
HCO2 , H2citrate , CH3NH3 , (CH3)2NH2  350 0.964 0.926 0.900 0.81 0.76
K, Cl, Br, I, CN, NO 
2 , NO3 300 0.964 0.925 0.899 0.805 0.755
  
Rb , Cs , NH4 , Tl , Ag  250 0.964 0.924 0.898 0.80 0.75
Charge ⴝ ⴞ2
Mg2, Be2 800 0.872 0.755 0.69 0.52 0.45
CH2(CH2CH2CO 
2 )2, (CH2CH2CH2CO2 )2 700 0.872 0.755 0.685 0.50 0.425
Ca , Cu , Zn , Sn , Mn , Fe , Ni2, Co2, C6H4(CO
2 2 2 2 2 2
2 )2,
H2C(CH2CO 2 )2, (CH2CH2CO2 )2
 600 0.870 0.749 0.675 0.485 0.405
Sr2, Ba2, Cd2, Hg2, S2, S2O2 2  
4 , WO4 , H2C(CO2 )2, (CH2CO2 )2,
(CHOHCO2 )2  500 0.868 0.744 0.67 0.465 0.38
Pb2, CO2 2 2 2 2
3 , SO3 , MoO4 , Co(NH3)5Cl , Fe(CN)5NO , C2O4 ,
2

Hcitrate2 450 0.867 0.742 0.665 0.455 0.37

Hg2 2 2 2 2 2 2
2 , SO4 , S2O3 , S2O6 , S2O8 , SeO4 , CrO4 , HPO4
2 400 0.867 0.740 0.660 0.445 0.355
Charge ⴝ ⴞ3
Al3, Fe3, Cr3, Sc3, Y3, In3, lanthanidesa 900 0.738 0.54 0.445 0.245 0.18
citrate3 500 0.728 0.51 0.405 0.18 0.115
PO3 3 3 3 3
4 , Fe(CN)6 , Cr(NH3)6 , Co(NH3)6 , Co(NH3)5H2O 400 0.725 0.505 0.395 0.16 0.095
Charge ⴝ ⴞ4
Th4, Zr4, Ce4, Sn4 1 100 0.588 0.35 0.255 0.10 0.065
Fe(CN)4
6 500 0.57 0.31 0.20 0.048 0.021
a. Lanthanides are elements 57–71 in the periodic table.
SOURCE: J. Kielland, J. Am. Chem. Soc. 1937, 59, 1675.

144 CHAPTER 8 Activity and the Systematic Treatment of Equilibrium

 The ion size  in Equation 8-6 is an empirical parameter that provides agreement
between measured activity coefficients and ionic strength up to ⬇ 0.1 M. In theory,  is
the diameter of the hydrated ion.8 However, sizes in Table 8-1 cannot be taken literally. For
example, the diameter of Cs ion in crystals is 340 pm. The hydrated Cs ion must be larger
than the ion in the crystal, but the size of Cs in Table 8-1 is only 250 pm.
Even though ion sizes in Table 8-1 are empirical parameters, trends among sizes are sensi-
ble. Small, highly charged ions bind solvent more tightly and have larger effective sizes than do
larger or less highly charged ions. For example, the order of sizes in Table 8-1 is Ionic and hydrated ion sizes are shown at the
Li 7 Na 7 K 7 Rb, even though crystallographic radii are Li 6 Na 6 K 6 Rb. opening of this chapter.

Effect of Ionic Strength, Ion Charge,

and Ion Size on the Activity Coefficient
Over the range of ionic strengths from 0 to 0.1 M, the effect of each variable on activity coef- 1.0
ficients is as follows:
M±
1. As ionic strength increases, the activity coefficient decreases (Figure 8-4). The activity 0.8

Activity coefficient (γ)

coefficient () approaches unity as the ionic strength ( ) approaches 0. M2±
2. As the magnitude of the charge of the ion increases, the departure of its activity 0.6
coefficient from unity increases. Activity corrections are more important for ions with a M3±

charge of 3 than for ions with a charge of 1 (Figure 8-4). 0.4 M4±
3. The smaller the ion size () , the more important activity effects become.
0.2
Example Using Table 8-1
Find the activity coefficient of Ca2 in a solution of 3.3 mM CaCl2. 0.0
0.001 0.01 0.1
Ionic strength (µ)
Solution The ionic strength is
Figure 8-4 Activity coefficients for differently
5[Ca2]
22  [Cl]
(1) 2 6
1
 charged ions with a constant ionic size () of
2 500 pm. At zero ionic strength,   1. The
greater the charge of the ion, the more rapidly
5(0.003 3)
4  (0.006 6)
16  0.010 M
1
  decreases as ionic strength increases. Note
2 that the abscissa is logarithmic.

In Table 8-1, Ca2 is listed under the charge 2 and has a size of 600 pm. Thus   0.675
when  0.010 M.

How to Interpolate
If you need to find an activity coefficient for an ionic strength that is between values in Table Interpolation is the estimation of a number that
8-1, you can use Equation 8-6. Alternatively, in the absence of a spreadsheet, it is usually eas- lies between two values in a table. Estimating a
ier to interpolate than to use Equation 8-6. In linear interpolation, we assume that values number that lies beyond values in a table is
called extrapolation.
between two entries of a table lie on a straight line. For example, consider a table in which
y  0.67 when x  10 and y  0.83 when x  20. What is the value of y when x  16?

Unknown y interval
x value y value y = 0.83
∆y y=?
Known x
10 0.67 interval
y = 0.67
16 ?
20 0.83
x = 10 x = 16 x = 20

∆x

To interpolate a value of y, we can set up a proportion:

Unknown y interval known x interval

Interpolation:  (8-7) This calculation is equivalent to saying:
y x
“16 is 60% of the way from 10 to 20. Therefore
the y value will be 60% of the way from 0.67
0.83  y 20  16 to 0.83.”
 1 y  0.766
0.83  0.67 20  10
For x  16, our estimate of y is 0.766.

8-2 Activity Coefficients 145

 2.5
Example Interpolating Activity Coefficients

Calculate the activity coefficient of H when  0.025 M.

Activity coefficient of H+

2.0
Solution H is the first entry in Table 8-1.
1.5  for H
0.01 0.914
1.0
0.025 ?
0.05 0.86
0.5
0 1 2 3
µ (M)
The linear interpolation is set up as follows:

Figure 8-5 Activity coefficient of H in

Unknown  interval known interval

solutions containing 0.010 0 M HClO4 and  
varying amounts of NaClO4. [Data derived from
0.86   0.05  0.025
L. Pezza, M. Molina, M. de Moraes, C. B. Melios, and 
J. O. Tognolli, Talanta 1996, 43, 1689.] The authoritative 0.86  0.914 0.05  0.01
source on electrolyte solutions is H. S. Harned ⬇   0.894
and B. B. Owen, The Physical Chemistry of
Electrolyte Solutions (New York: Reinhold, 1958). Another Solution A better and slightly more tedious calculation uses Equation 8-6, with
the ion size   900 pm listed for H in Table 8-1:
(0.51)(12 ) 20.025
log H   0.05498
1  (900 20.025 / 305)
H  100.05498  0.881

Activity Coefficients of Nonionic Compounds

Neutral molecules, such as benzene and acetic acid, have no ionic atmosphere because they
have no charge. To a good approximation, their activity coefficients are unity when the ionic
strength is less than 0.1 M. In this book, we set   1 for neutral molecules. That is, the
For neutral species, AC ⬇ [C]. A more accurate activity of a neutral molecule will be assumed to be equal to its concentration.
relation is log   k , where k ⬇ 0 for ion pairs, For gases such as H2, the activity is written
k ⬇ 0.11 for NH3 and CO2, and k ⬇ 0.2 for
organic molecules. For an ionic strength of A H2  PH2H2
 0.1 M,  ⬇ 1.00 for ion pairs,  ⬇ 1.03
for NH3, and  ⬇ 1.05 for organic molecules.
where PH2 is pressure in bars. The activity of a gas is called its fugacity, and the activity coef-
ficient is called the fugacity coefficient. Deviation of gas behavior from the ideal gas law
results in deviation of the fugacity coefficient from unity. For gases at or below 1 bar,  ⬇ 1.
For gases, A ⬇ P (bar). Therefore, for all gases, we will set A  P(bar) .

High Ionic Strengths

At high ionic strength, ␥ increases with Above an ionic strength of approximately 1 M, activity coefficients of most ions increase, as
increasing . shown for H in NaClO4 solutions in Figure 8-5. We should not be too surprised that activity
coefficients in concentrated salt solutions are not the same as those in dilute aqueous solu-
tion. The “solvent” is no longer H2O but, rather, a mixture of H2O and NaClO4. Hereafter, we
limit our attention to dilute aqueous solutions.

Example Using Activity Coefficients

Find the concentration of Ca2 in equilibrium with 0.050 M NaF saturated with CaF2. The
solubility of CaF2 is small, so the concentration of F is 0.050 M from NaF.

Solution We find [Ca2] from the solubility product expression, including activity coef-
ficients. The ionic strength of 0.050 M NaF is 0.050 M. At  0.050 0 M in Table 8-1,
we find Ca2  0.485 and F  0.81.
Note that the activity coefficient of F is Ksp  [Ca2]Ca2[F]22F
squared.
3.9 1011  [Ca2](0.485)(0.050) 2 (0.81) 2
[Ca2]  4.9 108 M

146 CHAPTER 8 Activity and the Systematic Treatment of Equilibrium

 8-3 pH Revisited
The definition pH ⬇ log[H] in Chapter 6 is not exact. The real definition is

pH  log A H  log[H]H (8-8) The real definition of pH!

When we measure pH with a pH meter, we are measuring the negative logarithm of the
hydrogen ion activity, not its concentration.

Example pH of Pure Water at 25C

Let’s calculate the pH of pure water by using activity coefficients.

Solution The relevant equilibrium is

KW
H2O ∆ H  OH (8-9)
Kw  A HA OH  [H]H[OH]OH (8-10)
H and OH are produced in a 1:1 mole ratio, so their concentrations must be equal.
Calling each concentration x, we write
Kw  1.0 1014  (x)H (x)OH
But the ionic strength of pure water is so small that it is reasonable to guess that
H  OH   1. Using these values in the preceding equation gives
1.0 1014  x2 1 x  1.0 107 M
The concentrations of H and OH are both 1.0 107 M. The ionic strength is 1.0
107 M, so each activity coefficient is very close to 1.00. The pH is
pH  log[H]H  log(1.0 107 )(1.00)  7.00

Example pH of Water Containing a Salt

Now let’s calculate the pH of water containing 0.10 M KCl at 25°C.

Solution Reaction 8-9 tells us that [H]  [OH]. However, the ionic strength of
0.10 M KCl is 0.10 M. The activity coefficients of H and OH in Table 8-1 are 0.83 and
0.76, respectively, when  0.10 M. Putting these values into Equation 8-10 gives
Kw  [H]H[OH]OH
1.0 1014  (x)(0.83)(x)(0.76)
x  1.26 107 M
The concentrations of H and OH are equal and are both greater than 1.0 107 M.
The activities of H and OH are not equal in this solution:
A H  [H]H  (1.26 107 )(0.83)  1.05 107
A OH  [OH]OH  (1.26 107 )(0.76)  0.96 107
Finally, we calculate pH  log A H  log(1.05 107 )  6.98.

The pH of water changes from 7.00 to 6.98 when we add 0.10 M KCl. KCl is not an acid
or a base. The pH changes because KCl affects the activities of H and OH. The pH change
of 0.02 unit lies at the limit of accuracy of pH measurements and is hardly important. How-
ever, the concentration of H in 0.10 M KCl (1.26 107 M) is 26% greater than the con-
centration of H in pure water (1.00 107 M).

8-4 Systematic Treatment of Equilibrium

The systematic treatment of equilibrium is a way to deal with all types of chemical equilibria,
regardless of their complexity. After setting up general equations, we often introduce specific
conditions or judicious approximations that allow simplification. Even simplified calcula-
tions are usually very tedious, so we make liberal use of spreadsheets for numerical

8-4 Systematic Treatment of Equilibrium 147

 solutions. When you have mastered the systematic treatment of equilibrium, you should be
able to explore the behavior of complex systems.
The systematic procedure is to write as many independent algebraic equations as there
are unknowns (species) in the problem. The equations are generated by writing all the chem-
ical equilibrium conditions plus two more: the balances of charge and of mass. There is only
one charge balance in a given system, but there could be several mass balances.

Charge Balance
Solutions must have zero total charge. The charge balance is an algebraic statement of electroneutrality: The sum of the positive
charges in solution equals the sum of the negative charges in solution.
Suppose that a solution contains the following ionic species: H, OH, K, H2PO 4,
HPO2
4 , and PO 3. The charge balance is
4

[H]  [K]  [OH]  [H2PO

4 ]  2[HPO4 ]  3[PO4 ]
2 3 (8-11)
This statement says that the total charge contributed by H and K equals the magnitude of
The coefficient of each term in the charge the charge contributed by all of the anions on the right side of the equation. The coefficient in
balance equals the magnitude of the charge front of each species always equals the magnitude of the charge on the ion. This statement is
on each ion. true because a mole of, say, PO3 contributes three moles of negative charge. If
4
[PO3
4 ]  0.01 M , the negative charge is 3[PO 3]  3(0.01)  0.03 M.
4
Equation 8-11 appears unbalanced to many people. “The right side of the equation has
much more charge than the left side!” you might think. But you would be wrong.
For example, consider a solution prepared by weighing out 0.025 0 mol of KH2PO4 plus
0.030 0 mol of KOH and diluting to 1.00 L. The concentrations of the species at equilibrium
are calculated to be
PO34 – [H]  5.1 1012 M 4 ]  1.3
[H2PO 106 M
[K]  0.055 0 M 4 ]  0.022 0 M
[HPO2
HPO 24 –
[OH]  0.002 0 M 4 ]  0.003 0 M
[PO3
H2PO4–
This calculation, which you should be able to do when you have finished studying acids and
OH– bases, takes into account the reaction of OH with H2PO 2
4 to produce HPO4 and PO4 .
3

Are the charges balanced? Yes, indeed. Plugging into Equation 8-11, we find
K+
[H]  [K]  [OH]  [H2PO
4 ]  2[HPO4 ]  3[PO4 ]
2 3
H+
5.1 1012  0.055 0  0.002 0  1.3 106  2(0.022 0)  3(0.003 0)
–0.06 –0.04 –0.02 0.00 0.02 0.04 0.06
Charge (M) 0.055 0 M  0.055 0 M

Figure 8-6 Charge contributed by each The total positive charge is 0.055 0 M, and the total negative charge also is 0.055 0 M
ion in 1.00 L of solution containing 0.025 0 mol (Figure 8-6). Charges must balance in every solution. Otherwise, a beaker with excess pos-
KH2PO4 plus 0.030 0 mol KOH. The total positive itive charge would glide across the lab bench and smash into another beaker with excess
charge equals the total negative charge. negative charge.
The general form of the charge balance for any solution is

g [positive charges]  g [negative charges] Charge balance: n1[C1]  n2[C2]  p  m1[A1]  m2[A2]  p (8-12)
Activity coefficients do not appear in the
charge balance. The charge contributed by where [C] is the concentration of a cation, n is the charge of the cation, [A] is the concentra-
0.1 M H is exactly 0.1 M. Think about this.
tion of an anion, and m is the magnitude of the charge of the anion.

Example Writing a Charge Balance

Write the charge balance for a solution containing H2O, H, OH, ClO 3
4 , Fe(CN) 6 ,
 3 2
CN , Fe , Mg , CH3OH, HCN, NH3, and NH4 . 

Solution Neutral species (H2O, CH3OH, HCN, and NH3 ) contribute no charge, so the
charge balance is
[H]  3[Fe3]  2[Mg2]  [NH4]  [OH]  [ClO
4 ]  3[Fe(CN) 6 ]  [CN ]
3 

Mass Balance
The mass balance is a statement of the
conservation of matter. It really refers to The mass balance, also called the material balance, is a statement of the conservation of
conservation of atoms, not to mass. matter. The mass balance states that the quantity of all species in a solution containing a

148 CHAPTER 8 Activity and the Systematic Treatment of Equilibrium

particular atom (or group of atoms) must equal the amount of that atom (or group) deliv-
ered to the solution. It is easier to see this relation through examples than by a general
statement.
Suppose that a solution is prepared by dissolving 0.050 mol of acetic acid in water to
give a total volume of 1.00 L. The acetic acid partially dissociates into acetate:

2  H
CH3CO2H T CH3CO 

Acetic acid Acetate

The mass balance states that the quantity of dissociated and undissociated acetic acid in the
solution must equal the amount of acetic acid put into the solution.
Mass balance for 0.050 M  [CH3CO2H]  [CH3CO
2]
acetic acid in water: What we put into Undissociated Dissociated
the solution product product

When a compound dissociates in several ways, the mass balance must include all the Activity coefficients do not appear in the mass
products. Phosphoric acid (H3PO4 ), for example, dissociates to H2PO 2 3
4 , HPO4 , and PO4 .
balance. The concentration of each species
The mass balance for a solution prepared by dissolving 0.025 0 mol of H3PO4 in 1.00 L is counts exactly the number of atoms of that
species.
0.025 0 M  [H3PO4]  [H2PO
4 ]  [HPO4 ]  [PO4 ]
2 3

Example Mass Balance When the Total Concentration Is Known

Write the mass balances for K and for phosphate in a solution prepared by mixing
0.025 0 mol KH2PO4 plus 0.030 0 mol KOH and diluting to 1.00 L.

Solution The total K is 0.025 0 M  0.030 0 M, so one mass balance is

[K]  0.055 0 M
The total of all forms of phosphate is 0.025 0 M, so the mass balance for phosphate is
[H3PO4]  [H2PO
4 ]  [HPO4 ]  [PO4 ]  0.025 0 M
2 3

Now consider a solution prepared by dissolving La(IO3 ) 3 in water.

Ksp
La(IO3 ) 3 (s) ∆ La3  3IO
3
Iodate

We do not know how much La3 or IO 3 is dissolved, but we do know that there must be
three iodate ions for each lanthanum ion dissolved. That is, the iodate concentration must be
three times the lanthanum concentration. If La3 and IO 3 are the only species derived from
La(IO3 ) 3, then the mass balance is

3 ]  3[La ]
[IO 3

If the solution also contains the ion pair LaIO2 2

3 and the hydrolysis product LaOH , the
mass balance would be
[Total iodate]  3[total lanthanum]
[IO3 ]  [LaIO2
3 ]  35[La ]  [LaIO3 ]  [LaOH ]6
3 2 2

Example Mass Balance When the Total Concentration Is Unknown

Write the mass balance for a saturated solution of the slightly soluble salt Ag3PO4, which
produces PO3 
4 and 3Ag when it dissolves.

Solution If the phosphate in solution remained as PO3

4 , we could write

[Ag]  3[PO3
4 ]

because three silver ions are produced for each phosphate ion. However, phosphate reacts
with water to give HPO2 
4 , H2PO4 , and H3PO4, so the mass balance is

[Ag]  35[PO3
4 ]  [HPO4 ]  [H2PO4 ]  [H3PO4]6
2  Atoms of Ag  3(atoms of P)

That is, the number of atoms of Ag must equal three times the total number of atoms of Box 8-2 illustrates the operation of a mass
phosphorus, regardless of how many species contain phosphorus. balance in natural waters.

8-4 Systematic Treatment of Equilibrium 149

Box 8-2 Calcium Carbonate Mass Balance in Rivers
Don
Ca2 is the most common cation in rivers and lakes. It comes Rio Grande
Mackenzie Danube
from dissolution of the mineral calcite by the action of CO2 to Dvina
Rhine
produce 2 moles of HCO 2 100 Nile Yukon Mississippi
3 for each mole of Ca :
Columbia St. Lawrence
CaCO3 (s)  CO2 (aq)  H2O T Ca2  2HCO3 (A) Niger World
Calcite Bicarbonate
Parana Fraser
Near neutral pH, most of the product is bicarbonate, not Pechora

[HCO 3− ] (mg /L)

Amazon Congo
CO23 or H2CO3. The mass balance for the dissolution of calcite is Orinoco
therefore [HCO 3 ] ⬇ 2[Ca ]. Indeed, measurements of Ca
2 2 and Uruguay

HCO3 in many rivers conform to this mass balance, shown by the
10

−
]
straight line on the graph. Rivers such as the Danube, the Missis-

3
O
C
sippi, and the Congo, which lie on the line [HCO 3 ]  2[Ca ],
2
[Ca2 + ] = 20 mg/L

[H
]=
2+
appear to be saturated with calcium carbonate. If the river water for normal

a
C
atmospheric
were in equilibrium with atmospheric CO2 (PCO2  103.4 bar), the

2[
PCO = 10 − 3.4 bar
concentration of Ca2 would be 20 mg/L (see Problem 8-28). 2

Rivers with more than 20 mg of Ca2 per liter have a higher con-
centration of dissolved CO2 produced by respiration or from
inflow of groundwaters with a high CO2 content. Rivers such as 1
1 10 100
the Nile, the Niger, and the Amazon, for which 2[Ca2] 6 [Ca2 + ] (mg/L)
[HCO3 ], are not saturated with CaCO3.
Just between 1960 and 2000, CO2 in the atmosphere increased Concentrations of bicarbonate and calcium in many rivers conform to
3 ] ⬇ 2[Ca ]. [Data from W. Stumm and
the mass balance for Reaction A: [HCO 2
by 17% (Box 20-1)—mostly from our burning of fossil fuel. This
increase drives Reaction A to the right and threatens the existence of J. J. Morgan, Aquatic Chemistry, 3rd ed. (New York: Wiley-lnterscience, 1996), p. 189;
and H. D. Holland, The Chemistry of the Atmosphere and Oceans (New York: Wiley-
coral reefs,9 which are huge, living structures consisting largely
Interscience, 1978).]
of CaCO3. Coral reefs are a unique habitat for many aquatic species.

Systematic Treatment of Equilibrium

Now that we have considered the charge and mass balances, we are ready for the systematic
treatment of equilibrium.10 Here is the general prescription:
Step l Write the pertinent reactions.
Step 2 Write the charge balance equation.
Step 3 Write mass balance equations. There may be more than one.
Step 4 Write the equilibrium constant expression for each chemical reaction. This step is
the only one in which activity coefficients appear.
Step 5 Count the equations and unknowns. There should be as many equations as
unknowns (chemical species). If not, you must either find more equilibria or fix
some concentrations at known values.
Step 6 By hook or by crook, solve for all the unknowns.
Steps 1 and 6 are the heart of the problem. Guessing what chemical equilibria exist in a
given solution requires a fair degree of chemical intuition. In this book, you will usually be
given help with step 1. Unless we know all the relevant equilibria, it is not possible to calcu-
late the composition of a solution correctly. Because we do not know all the chemical reac-
tions, we undoubtedly oversimplify many equilibrium problems.
Step 6 is likely to be your biggest challenge. With n equations involving n unknowns,
the problem can always be solved, at least in principle. In the simplest cases, you can do this
by hand; but for most problems, approximations are made or a spreadsheet is employed.

8-5 Applying the Systematic

Treatment of Equilibrium
The systematic treatment of equilibrium is best understood by studying some examples.

A Simple Example: Ionization of Water

The dissociation of water into H and OH occurs in every aqueous solution:
Kw
H2O ∆ H  OH Kw  1.0 1014 at 25°C (8-13)

150 CHAPTER 8 Activity and the Systematic Treatment of Equilibrium

Let’s apply the systematic treatment to find the concentrations of H and OH in pure water.
Step 1 Pertinent reactions. The only one is Reaction 8-13.
Step 2 Charge balance. The only ions are H and OH, so the charge balance is
[H]  [OH] (8-14)
Step 3 Mass balance. Reaction 8-13 creates one H for each OH. The mass balance is
simply [H]  [OH], which is the same as the charge balance for this system.
Step 4 Equilibrium constant expression.
Kw  [H]H[OH]OH  1.0 1014 (8-15)
This is the only step in which activity coefficients enter the problem.
Step 5 Count equations and unknowns. We have two equations, 8-14 and 8-15, and two We need n equations to solve for n unknowns.
unknowns, [H] and [OH].
Step 6 Solve.
Now we must decide what to do about the activity coefficients. We expect that the ionic
strength ( ) of pure water will be very low. Therefore, it is reasonable to suppose that H Recall that ␥ approaches 1 as
and OH are both unity. approaches 0.
Putting [H]  [OH] into Equation 8-15 gives
[H]H[OH]OH  1.0 1014
[H]
1
[H]
1  1.0 1014 The ionic strength is 107 M. The assumption
[H]  1.0 107 M that H  OH  1 is good.

Also, [OH]  [H]  1.0 107 M. As a reminder, the pH is given by

pH  log A H  log[H]H  log(1.0 107 )(1)  7.00 This is the correct definition of pH. When we
neglect activity coefficients, we will write
pH  log[H].
Solubility of Calcium Sulfate
Our goal is to find the concentrations of the major species in a saturated solution of CaSO4.
Step l Pertinent reactions. Even in such a simple system, there are quite a few reactions:
Ksp
CaSO4 (s) ∆ Ca2  SO2
4 Ksp  2.4 105 (8-16) Caveat Emptor! In all equilibrium problems, we
Kion pair are limited by how much of the system’s
CaSO4 (s) ∆ CaSO4 (aq) Kion pair  5.0 103 (8-17) chemistry is understood. Unless we know all
Kacid
Ca2  H2O ∆ CaOH  H Kacid  2.0 1013 (8-18) the relevant equilibria, it is impossible to
Kbase calculate the composition.
4  H2O ∆ HSO4  OH Kbase  9.8
SO2   1013 (8-19)
Kw
H2O ∆ H  OH Kw  1.0 1014 (8-20)
There is no way you can be expected to come up with all of these reactions, so you
will be given help with this step.
Step 2 Charge balance. Equating positive and negative charges gives
2[Ca2]  [CaOH]  [H]  2[SO2
4 ]  [HSO4 ]  [OH ]
  (8-21) Multiply [Ca2] and [SO2
4 ] by 2 because 1 mol
of each ion has 2 mol of charge.
Step 3 Mass balance. Reaction 8-16 produces 1 mole of sulfate for each mole of calcium.
No matter what happens to these ions, the total concentration of all species with
sulfate must equal the total concentration of all species with calcium:
[Total calcium]  [total sulfate]
[Ca2]  [CaSO4 (aq)]  [CaOH]  [SO2
4 ]  [HSO4 ]  [CaSO4 (aq)]
 (8-22)
Step 4 Equilibrium constant expressions. There is one for each chemical reaction.
Ksp  [Ca2]Ca2[SO2
4 ]SO42 2.4 105 (8-23)
Kion pair  [CaSO4 (aq)]  5.0 103 (8-24) The activity coefficient of the neutral species
CaSO4(aq) is 1.
[CaOH]CaOH[H]H
Kacid   2.0 1013 (8-25)
[Ca2]Ca2
[HSO 
4 ]HSO4[OH ]OH
Kbase   9.8 1013 (8-26)
[SO2
4 ]SO2
4

Kw  [H]H[OH]OH  1.0 1014 (8-27)

Step 4 is the only one where activity coefficients come in.

8-5 Applying the Systematic Treatment of Equilibrium 151

 Step 5 Count equations and unknowns. There are seven equations (8-21 through 8-27) and
seven unknowns: [Ca2], [SO2   
4 ], [CaSO4 (aq)], [CaOH ], [HSO4 ], [H ], and
[OH]. In principle, we have all the information necessary to solve the problem.
Step 6 Solve. Well, this is not easy! We don’t know the ionic strength, so we cannot evalu-
ate activity coefficients. Also, where do we start when there are seven unknowns?
Just when the world looks grim, a Good Chemist comes galloping down the hill on her
white stallion to rescue us with some hints. “First of all,” she says, “Reactions 8-18 and 8-19
have small equilibrium constants, so they are not very important compared with Reactions
8-16 and 8-17. As for activity coefficients, you can begin by setting them all equal to 1 and
solving for all concentrations. Then you can calculate the ionic strength and find values for
the activity coefficients. With these coefficients, you can solve the problem a second time
and find a new set of concentrations. You can repeat this process a few times until reaching a
constant answer.”
On the advice of the Good Chemist, we neglect the acid-base reactions 8-18 and 8-19.
The remaining reactions of calcium sulfate, 8-16 and 8-17, are not reactions with H2O.
Therefore, in our approximation, Reaction 8-20 is independent of the calcium sulfate chem-
istry. Reaction 8-20 produces [H] and [OH], which we know are 1 107 M. These con-
centrations of H and OH are not exactly correct, because we have neglected Reactions
8-18 and 8-19, which do play a role in determining [H] and [OH].
These approximations leave just Reactions 8-16 and 8-17. In the charge balance 8-21,
CaOH and HSO 4 are neglected. Also, [H ]  [OH ], so they cancel. The charge balance
 

becomes 2[Ca2]  2[SO24]. In the mass balance 8-22, we discard CaOH and HSO 4
because we neglect Reactions 8-18 and 8-19. The term [CaSO4 (aq)] cancels, leaving
[Ca2]  [SO2 4 ], which is the same as the charge balance. We have three unknowns
([Ca2], [SO24 ], [CaSO4 (aq)]) and three equations:

Ksp  [Ca2]Ca2[SO2
4 ]SO42  2.4 105 (8-23)
Kion pair  [CaSO4 (aq)]  5.0 103 (8-24)
[Ca2]  [SO2
4 ] (8-28)
Equation 8-24 says [CaSO4 (aq)]  5.0 103 M, so [CaSO4 (aq)] is known.
The simplified problem is reduced to Equations 8-23 and 8-28. We find a first approxi-
mate solution by setting activity coefficients to 1:
[Ca2]1Ca2[SO2
4 ]1SO2
4
 2.4 105 (8-29)
4 ]1 (l)  2.4
[Ca2]1 (l)[SO2 105
4 ]  [Ca ]
[SO2 2 [Ca2]1 (l)[Ca2]1 (l)  2.4 l05 1 [Ca2]1  4.9 103 M
where the subscript 1 means it is our first approximation. If [Ca2]  [SO2 4 ]  4.9
103 M, then the ionic strength is  4(4.9 103 M)  0.020 M. Interpolating in Table
8-1, we find the activity coefficients Ca2  0.628 and SO2
4
 0.606. Putting these coeffi-
We are carrying out a method of successive cients back into Equation 8-29 provides a second approximation:
approximations. Each cycle is called an
iteration. [Ca2]2 (0.628)[Ca2]2 (0.606)  2.4 105 1 [Ca2]2  7.9 103 M
1  0.032 M
Repeating this process gives the following results:
Iteration Ca2 ⴙ SO24ⴚ [Ca2] (M) (M)
1 1 1 0.004 9 0.020
2 0.628 0.606 0.007 9 0.032
3 0.570 0.542 0.008 8 0.035
4 0.556 0.526 0.009 1 0.036
5 0.551 0.520 0.009 2 0.037
Total concentration of dissolved sulfate 6 0.547 0.515 0.009 2 0.037
4 ]  [CaSO4(aq)]
 [SO2
 0.009 2  0.005 0  0.014 2 M The 6th iteration gives the same concentration as the 5th, so we have reached a constant
which is not too far from the measured value in
answer.
Figure 6-1. With the extended Debye-Hückel With the advice of the Good Chemist, we simplified the problem tremendously. Now
equation, instead of interpolation, total we need to know if her advice was good. From [Ca2]  [SO2 4 ]  0.009 2 M and
dissolved sulfate  0.014 7 M. [H]  [OH]  1.0 107 M, we can estimate [CaOH] and [HSO 4 ] to see if they are

152 CHAPTER 8 Activity and the Systematic Treatment of Equilibrium

negligible. We are just looking for orders of magnitude, so we ignore activity coefficients.
From Equation 8-25, we have
[CaOH][H]
 2.0 1013 (8-25)
[Ca2]
(2.0 1013 )[Ca2] (2.0 1013 )[0.009 2]
[CaOH] ⬇ 
 2 108 M
[H ] [1.0 107]
From Equation 8-26, we estimate
(9.8 1013 )[SO2
4 ] (9.8 1013 )[0.009 2]
4] ⬇
[HSO 
 9 108 M
[OH ] [1.0 107]
Both [CaOH] and [HSO 4 ] are ⬃10 times less than [Ca ] and [SO4 ], so it was reason-
5 2 2
 
able to neglect [CaOH ] and [HSO4 ] in the charge and mass balances.

We Will Usually Omit Activity Coefficients

Although it is proper to write equilibrium constants in terms of activities, the complexity of
manipulating activity coefficients is a nuisance. Most of the time, we will omit activity coef-
ficients unless there is a particular point to be made. Occasional problems will remind you
how to use activities.

Solubility of Magnesium Hydroxide

Let’s find the concentrations of species in a saturated solution of Mg(OH) 2, given the fol-
lowing chemistry. For simplicity, we ignore activity coefficients.
Ksp
Mg(OH) 2 (s) ∆ Mg2  2OH Ksp  [Mg2][OH]2  7.1 1012 (8-30)
K1 [MgOH]
Mg2  OH ∆ MgOH K1   3.8 102 (8-31)
[Mg2][OH]
Kw
H2O ∆ H  OH Kw  [H][OH]  1.0 1014 (8-32)
Step 1 Pertinent reactions are listed above.
Step 2 Charge balance: 2[Mg2]  [MgOH]  [H]  [OH] (8-33)
Step 3 Mass balance. This is a little tricky. From Reaction 8-30, we could say that the con-
centrations of all species containing OH equal two times the concentrations of all
magnesium species. However, Reaction 8-32 also creates 1 OH for each H. The
mass balance accounts for both sources of OH:
[OH]  [MgOH]  25[Mg2]  [MgOH]6  [H] (8-34)
144424443 144424443
Species containing OH Species containing Mg2

After all this work, Equation 8-34 is equivalent to Equation 8-33.

Step 4 Equilibrium constant expressions are in Equations 8-30 through 8-32.
Step 5 Count equations and unknowns. We have four equations (8-30 to 8-33) and four
unknowns: [Mg2], [MgOH], [H], and [OH].
Step 6 Solve.
Before hitting the algebra, we can make one simplification. The solution must be very
basic because we made it from Mg(OH) 2. In basic solution, [OH] W [H], so we can
neglect [H] on the left side of Equation 8-33 in comparison with [OH] on the right side.
The charge balance simplifies to
2[Mg2]  [MgOH]  [OH] (8-35)
From the K1 expression 8-31, we write [MgOH]  K1[Mg2][OH]. Substituting this
expression for [MgOH] into Equation 8-35 gives
2[Mg2]  K1[Mg2][OH]  [OH]
which we solve for [Mg2]:
[OH]
[Mg2] 
2  K1[OH]

8-5 Applying the Systematic Treatment of Equilibrium 153

Figure 8-7 Spreadsheet for solving A B C D
Equation 8-36.
1 Mg(OH)2 Solubility
2
_
3 Ksp = [OH]guess = [OH ]3/(2 + K1[OH]) =
4 7.1E-12 0.0002459 7.1000E-12
5 K1 =
6 3.8E+02 [Mg2+] = [MgOH+] =
7 0.0001174 0.0000110
8
9 D4 = C4^3/(2+A6*C4)
10 C7 = A4/C4^2
11 D8 = A6*C7*C4

Substituting this expression for [Mg2] into the solubility product reduces the equation to a
single variable:
[OH] [OH]3
Ksp  [Mg2][OH]2  a b[OH]2  (8-36)
2  K1[OH ]
 2  K1[OH]
We are down to solving the ugly Equation 8-36 for [OH]. Just when the world looks
grim again, the Good Chemist says, “Use a spreadsheet to vary [OH] until Equation 8-36 is
satisfied.” We do this in Figure 8-7, where we guess a value of [OH] in cell C4 and evaluate
the right side of Equation 8-36 in cell D4. When we have guessed the correct value of
[OH], cell D4 is equal to Ksp. A better procedure is to use Excel GOAL SEEK, described at
the end of Section 6-8, to vary cell C4 until cell D4 is equal to Ksp. (Before using GOAL SEEK,
The final result confirms the approximation we select OPTIONS from the TOOLS menu. Select the Calculations tab and set Maximum change
made. to1e-24.) Final results in the spreadsheet are [OH]  2.5 104 M, [Mg2]  1.2 104 M,
[H]  Kw /[OH]  4.1 1011 M V [OH] and [MgOH]  1.1 105 M. We also find pH  log[H]  log(Kw /[OH]) 10.39.

Terms to Understand
activity extended Debye-Hückel ionic strength
activity coefficient equation mass balance
charge balance ionic atmosphere pH

Summary
The thermodynamic equilibrium constant for the reaction by interpolation in Table 8-1. pH is defined in terms of the activity
aA  bB T cC  dD is K  A cC A dD /(A aAA bB), where A i is the of H: pH  log A H  log[H]H.
activity of the ith species. The activity is the product of the concen- In the systematic treatment of equilibrium, we write pertinent
tration (c) and the activity coefficient (): A i  cii. For nonionic equilibrium expressions, as well as the charge and mass balances.
compounds and gases, i ⬇ 1. For ionic species, the activity coeffi- The charge balance states that the sum of all positive charges in
cient depends on the ionic strength, defined as  12 兺ci z2i , where zi solution equals the sum of all negative charges. The mass balance
is the charge of an ion. The activity coefficient decreases as ionic states that the moles of all forms of an element in solution must
strength increases, at least for low ionic strengths (0.1 M). Disso- equal the moles of that element delivered to the solution. We make
ciation of ionic compounds increases with ionic strength because certain that we have as many equations as unknowns and then solve
the ionic atmosphere of each ion diminishes the attraction of ions for the concentrations by using algebra, approximations, spread-
for one another. You should be able to estimate activity coefficients sheets, magic, or anything else.

Exercises
8-A. Assuming complete dissociation of the salts, calculate 8-E. A 40.0-mL solution of 0.040 0 M Hg2 (NO3 ) 2 was titrated with
the ionic strength of (a) 0.2 mM KNO3; (b) 0.2 mM Cs2CrO4; 60.0 mL of 0.100 M KI to precipitate Hg2I2 (Ksp  4.6 1029 ).
(c) 0.2 mM MgCl2 plus 0.3 mM AlCl3. (a) What volume of KI is needed to reach the equivalence point?
(b) Calculate the ionic strength of the solution when 60.0 mL of KI
8-B. Find the activity (not the activity coefficient) of the
have been added.
(C3H7 ) 4N (tetrapropylammonium) ion in a solution containing
0.005 0 M (C3H7 ) 4NBr plus 0.005 0 M (CH3 ) 4NCl. 2 ( log A Hg22 ) for part (b).
(c) Using activities, calculate pHg2
8-F. (a) Write the mass balance for CaCl2 in water if the species are
8-C. Using activities, find [Ag] in 0.060 M KSCN saturated with
Ca2 and Cl.
AgSCN(s).
(b) Write the mass balance if the species are Ca2, Cl, CaCl, and
8-D. Using activities, calculate the pH and concentration of H in CaOH.
0.050 M LiBr at 25°C. (c) Write the charge balance for part (b).

154 CHAPTER 8 Activity and the Systematic Treatment of Equilibrium

8-G. Write the charge and mass balances for dissolving CaF2 in 8-I. (Warning: Long problem!) Using activities, find the con-
water if the reactions are centrations of the major species in 0.10 M NaClO4 saturated with
Mn(OH) 2. Take the ionic strength to be 0.10 M and suppose that
CaF2 (s) T Ca2  2F
the ion size of MnOH is the same as Mn2. Consider just the fol-
Ca2  H2O T CaOH  H lowing chemistry:
Ca2  F T CaF Ksp

CaF2 (s) T CaF2 (aq) Mn(OH) 2 (s) ∆ Mn2  2OH Ksp  1.6 1013
K1
F  H T HF(aq) Mn2  OH ∆ MnOH K1  2.5 103
HF(aq)  F T HF
2

8-H. Write charge and mass balances for aqueous Ca3 (PO4 ) 2 if the
species are Ca2, CaOH, CaPO 3 2 
4 , PO4 , HPO4 , H2PO4 , and H3PO4.

Problems
Activity Coefficients 8-13. The temperature-dependent form of the extended Debye-
8-1. Explain why the solubility of an ionic compound increases as Hückel equation 8-6 is
the ionic strength of the solution increases (at least up to ⬃0.5 M). (1.825 106 )(T ) 3/2z2 2
log  
8-2. Which statements are true: In the ionic strength range 0–0.1 1   2 /(2.00 2T)
M, activity coefficients decrease with (a) increasing ionic
strength; (b) increasing ionic charge; (c) decreasing hydrated where  is the (dimensionless) dielectric constant* of water, T is the
radius? temperature (K), z is the charge of the ion, is the ionic strength
(mol/L), and  is the ion size parameter (pm). The dependence of 
8-3. Calculate the ionic strength of (a) 0.008 7 M KOH and
on temperature is
(b) 0.000 2 M La(IO3 ) 3 (assuming complete dissociation at this low
concentration and no hydrolysis reaction to make LaOH2).   79.755e( 4.6 103) (T293.15)

8-4. Find the activity coefficient of each ion at the indicated ionic Calculate the activity coefficient of SO2
4 at 50.00°C when 
strength: 0.100 M. Compare your value with the one in Table 8-1.
(a) SO2
4 (  0.01 M)
8-14. Extended Debye-Hückel equation. Use Equation 8-6 to
(b) Sc3 (  0.005 M)
calculate the activity coefficient () as a function of ionic strength
(c) Eu3 (  0.1 M)
( ) for  0.000 1, 0.000 3, 0.001, 0.003, 0.01, 0.03, and 0.1 M.
(d) (CH3CH2 ) 3NH (  0.05 M)
(a) For an ionic charge of 1 and a size   400 pm, make a table
8-5. Interpolate in Table 8-1 to find the activity coefficient of H of  ( 10 ⵩ (log )) for each value of .
when  0.030 M. (b) Do the same for ionic charges of 2, 3, and 4.
8-6. Calculate the activity coefficient of Zn2 when  0.083 M (c) Plot  versus log to obtain a graph similar to Figure 8-5.
by using (a) Equation 8-6; (b) linear interpolation in Table 8-1.
Systematic Treatment of Equilibrium
8-7. Calculate the activity coefficient of Al3 when  0.083 M
by linear interpolation in Table 8-1. 8-15. State the meaning of the charge and mass balance equations.
8-8. The equilibrium constant for dissolution in water of a nonionic 8-16. Why do activity coefficients not appear in the charge and
compound, such as diethyl ether (CH3CH2OCH2CH3 ), can be mass balance equations?
written 8-17. Write a charge balance for a solution containing H, OH,
ether(l) T ether(aq) K  [ether(aq)]ether Ca2, HCO 2   
3 , CO3 , Ca(HCO3 ) , Ca(OH) , K , and ClO4 .


8-18. Write a charge balance for a solution of H2SO4 in water if the

At low ionic strength,  ⬇ 1 for neutral compounds. At high ionic H2SO4 ionizes to HSO 2
4 and SO4 .
strength, most neutral molecules can be salted out of aqueous solu-
tion. That is, when a high concentration (typically 7 1 M) of a salt 8-19. Write the charge balance for an aqueous solution of arsenic
such as NaCl is added to an aqueous solution, neutral molecules acid, H3AsO4, in which the acid can dissociate to H2AsO 4,
usually become less soluble. Does the activity coefficient, ether, HAsO2 3
4 , and AsO4 . Look up the structure of arsenic acid in
increase or decrease at high ionic strength? Appendix G and write the structure of HAsO2
4 .

8-9. Find [Hg2

2 ] in saturated Hg2Br2 in 0.001 00 M KBr.
8-10. Find the concentration of Ba2 in a 0.100 M (CH3 ) 4NIO3 *The dimensionless dielectric constant, , measures how well a solvent can separate
solution saturated with Ba(IO3 ) 2. oppositely charged ions. The force of attraction (newtons) between ions of charge q1
and q2 (coulombs) separated by distance r (meters) is
8-11. Find the activity coefficient of H
in a solution contain-
q1q2
ing 0.010 M HCl plus 0.040 M KClO4. What is the pH of the Force  (8.988 10 9)
r 2
solution?
The larger the value of , the smaller the attraction between ions. Water, with  ⬇ 80,
8-12. Using activities, calculate the pH of a solution containing separates ions very well. Here are some values of : methanol, 33; ethanol, 24; benzene,
0.010 M NaOH plus 0.012 0 M LiNO3. What would be the pH if 2; vacuum and air, 1. Ionic compounds dissolved in less polar solvents than water may
you neglected activities? exist predominantly as ion pairs, not separate ions.

Problems 155
8-20. (a) Write the charge and mass balances for a solution made by A B C
dissolving MgBr2 to give Mg2, Br, MgBr, and MgOH. 1 Spreadsheet for iterative LiF solubility computation
(b) Modify the mass balance if the solution was made by dissolving
2
0.2 mol MgBr2 in 1 L.
3 Size (pm) of Li + = Ionic strength =
8-21. This problem demonstrates what would happen if charge bal- 4 600 0.00000
ance did not exist in a solution. The force between two charges was 5 Size (pm) of F – = Activity coeff Li + =
given in the footnote to Problem 8-13. What is the force between 6 350 1
two beakers separated by 1.5 m if one contains 250 mL with 7 Ksp = Activity coeff F – =
1.0 106 M excess negative charge and the other has 250 mL 8 0.0017 1
with 1.0 106 M excess positive charge? There are 9.648 104 9 +
[Li ] = [F] =
coulombs per mole of charge. Convert the force from N into pounds 10 0.04123
with the factor 0.224 8 pounds/N.
11
8-22. For a 0.1 M aqueous solution of sodium acetate, NaCH3CO
2, 12 B6 = 10^((– 0.51)*SQRT(B4)/(1+A4*SQRT(B4)/305))
one mass balance is simply [Na]  0.1 M. Write a mass balance 13 B8 = 10^((– 0.51)*SQRT(B4)/(1+A6*SQRT(B4)/305))
involving acetate. 14 B10 = SQRT(A8/(B6*B8))
8-23. Consider the dissolution of the compound X2Y3, which gives
X2Y2 4 2
2 , X2Y , X2Y3 (aq), and Y . Use the mass balance to find
an expression for [Y2] in terms of the other concentrations. Sim-
plify your answer as much as possible. Because the ionic strength of a 1:1 electrolyte is equal to the
concentration, copy the value 0.041 23 from cell B10 into cell
8-24. Write a mass balance for a solution of Fe2 (SO4 ) 3 if the B4. (To transfer a numerical value, rather than a formula, COPY
species are Fe3, Fe(OH) 2, Fe(OH) 2, Fe2 (OH) 4  2
2 , FeSO4 , SO4 , cell B10 and then highlight cell B4. In the EDIT menu, select

and HSO4 . PASTE SPECIAL and then choose Value. The numerical value from
8-25. (a) Following the example of Mg(OH) 2 in Section 8-5, write B10 will be pasted into B4.) This procedure gives new activity
the equations needed to find the solubility of Ca(OH) 2. Include coefficients in cells B6 and B8 and a new concentration in cell
activity coefficients where appropriate. Equilibrium constants are in B10. Copy the new concentration from cell B10 into cell B4 and
Appendixes F and I. repeat this procedure several times until you have a constant
(b) Neglecting activity coefficients, compute the concentrations of answer.
all species and compute the solubility of Ca(OH) 2 in g/L. (c) Using circular references in Excel. Take your spreadsheet and
8-26. Look up the equilibrium constant for the ion-pairing reaction enter 0 in cell B4. The value 0.041 23 is computed in cell B10.
Zn2  SO2 4 T ZnSO4 (aq) in Appendix J.
Ideally, you would like to write “B10” in cell B4 so that the
(a) Use the systematic treatment of equilibrium to find [Zn2] in value from B10 would be copied to B4. Excel gives a “circular
0.010 F ZnSO4. Neglect activity coefficients and any other reactions. reference” error message because cell B10 depends on B4 and cell
(b) Use the answer from part (a) to compute the ionic strength and B4 depends on B10. To get around this problem, go to the TOOLS
activity coefficients of Zn2 and SO2 menu and choose OPTIONS. Select Calculation and choose Itera-
4 . Then repeat the calculation
using activity coefficients. Repeat the procedure two more times to tion. Set the maximum change to 0.000 01. Click OK and Excel
find a good estimate of [Zn2]. What percentage is ion paired? What merrily iterates between cells B10 and B4 until the two values
is the ionic strength of the solution? agree within 0.000 01.

8-27. Finding solubility by iteration. Use the systematic 8-28. Heterogeneous equilibria and calcite solubility. If river water
treatment of equilibrium to find the concentrations of the major in Box 8-2 is saturated with calcite (CaCO3 ), [Ca2] is governed by
species in a saturated aqueous solution of LiF. Consider the follow- the following equilibria:
ing reactions CaCO3 (s) T Ca2  CO2
3 Ksp  4.5 109
LiF(s) T Li  F Ksp  [Li]Li[F]F  0.001 7 CO2 (g) T CO2 (aq) KCO2  0.032
LiF(s) T LiF(aq) Kion pair  LiF(aq)LiF(aq)  0.002 9 CO2 (aq)  H2O T HCO
3  H
 K1  4.46 107
3 T CO3  H
HCO K2  4.69
2  1011
(a) Initially, set the ionic strength to 0 and solve for all the concen-
trations. Then compute the ionic strength and activity coefficients (a) From these reactions, find the equilibrium constant for the
and find new concentrations. Use several iterations to home in on reaction
the correct solution.
(b) In the systematic treatment, you will find that the calculation CaCO3 (s)  CO2 (aq)H2O T Ca2  2HCO
3 K? (A)
simplifies to [Li]  [F]  2Ksp /(LiF ) . Set up the following (b) The mass balance for Reaction A is [HCO 3 ]  2[Ca ]. Find
2

spreadsheet, in which ionic strength in cell B4 is initially given the 2

[Ca ] (in mol/L and in mg/L) in equilibrium with atmospheric
value 0. Activity coefficients in cells B6 and B8 are from the CO2 if PCO2  3.8 104 bar. Locate this point on the line in
extended Debye-Hückel equation. Cell B10 computes [Li]  Box 8-2. [Atmospheric CO2 is increasing so rapidly (Box 20-1)
[F]  2Ksp /(LiF ). With 0 in cell B4, your spreadsheet should that PCO2 needs to be revised between editions of this book. We
compute 1 in cells B6 and B8 and [Li]  [F]  0.041 23 M in are changing our environment—with consequences left to the
cell B10. next generation.]

156 CHAPTER 8 Activity and the Systematic Treatment of Equilibrium

(c) The concentration of Ca2 in the Don River is 80 mg/L. What La(NO3 ) 3 Ionic Potential
effective PCO2 is in equilibrium with this much Ca2? How can the (mL) strength (M) [F] (M) F (mV)
river have this much CO2?
0 0.060 0 0.060 0 0.80 58.0
8-29. (Warning: This is a long problem, best done by five people, 5.00
each completing one line of the table.) A fluoride ion-selective elec- 10.00
trode responds to fluoride activity above A F ⬇ 106 in the follow- 19.00
ing manner at 25°C: 20.00
Potential (mV)  constant  59.16 log A F 22.00

The constant depends on the reference electrode used with the fluo- If you use a spreadsheet for this exercise, compute activity coeffi-
ride electrode. A 20.00-mL solution containing 0.060 0 M NaF was cients with the extended Debye-Hückel equation and compute
titrated with 0.020 0 M La(NO3 ) 3 to precipitate LaF3. Just consider- many more points. (You can look up the results of a similar titration
ing the precipitation reaction, fill in the following table and plot the to compare with your calculations.11)
expected titration curve, assuming that the constant is 20.0 mV.

Problems 157