Activity and the Systematic

Treatment of Equilibrium
Chapter 8

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 1
Chapter Outline

• Section 8-1 The Effect of Ionic Strength on Solubility of Salts

• Section 8-2 Activity Coefficients
• Section 8-3 pH Revisited
• Section 8-4 Systematic Treatment of Equilibrium
• Section 8-5 Applying the Systematic Treatment of Equilibrium

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 2
Hydrated Ions (1 of 2)

• Ions and molecules in solution are

surrounded by an organized sheath of
solvent molecules.

• Smaller, more highly charged ions

• Bind more H2O molecules
• Behave as larger species in solution

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Estimated Number of Waters of Hydration

Molecule Tightly bound H2O Molecule Tightly bound H2O

CH3CH2CH3 0 O
C6H6 0 ∥
CH3CNHCH3 4
CH3CH2Cl 0
CH3NO2 5
CH3CH2SH NH4 0
CH3CO−
2 5
CH3—O―CH3 1
CH3NH2 6
CH3CH2OH 1
CH3SO3H 7
(CH3)2C=O 1.5
NH3 9
CH3CH=O 1.5
CH3SO−
3 10
CH3CO2H 2
NH4+ 12
CH3C≡N 3

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Hydrated Ions (2 of 2)

• Water binds to cations through the oxygen bonds.

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

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 Effect of Ionic Strength on Ionic Dissociation
Consider the following equilibrium reaction: Color Plate 4
Figure 8-1
Fe3+ + SCN − Fe(SCN) 2+
(pale yellow) (colorless) (red)

[Fe(SCN) 2+ ]
K=
[Fe3+ ][SCN − ]

The equilibrium “constant”

is not really constant

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 7
 Why does the solubility increase when salts are
added to the solution?
Ionic atmosphere
Figure 8-2
• Region of solution around an ion or charged
particle
• Contains an excess of the oppositely charged ions
The greater the ionic strength of solution, the higher
the charge on each ionic atmosphere.
• Cation and anion attraction is reduced (relative to
attraction in distilled water)
• Tendency of ions to come together is reduced
• Solubility of salt is increased
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Increasing Ionic Strength Promotes Dissociation

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 Effect of Added Salts on Solubility
HO Figure 8-3
OH HO OH

HO 2 CCHCHCO 2 K( s) HO 2 CCHCHCO 2− + K +
Potassiumn hydrogen tartrate
• Compare the effect on potassium
hydrogen tartrate solubility when each
compound is added to solution.
➢ KCl
➢ NaCl
➢ MgSO4
➢ Glucose
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 Ionic Strength
Ionic strength () is a measure of the total concertation of ions in solution.

1 1
μ = (c1 z12 + c2 z22 + c3 z32 + ) =  ci zi2
2 2

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 11
Example: Calculation of Ionic Strength (1 of 4)
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.

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 12
Example: Calculation of Ionic Strength (2 of 4)
Solution
1
(a) μ = {[Na + ]  (+1) 2 + [NO3− ]  ( −1) 2 }
2
1
= {0.10 1 + 0.10 1} = 0.10 M
2
1
(b) μ = {[Na + ]  (+1) 2 + [SO 24 − ]  ( −2) 2 }
2
1
= {(0.020 1) + (0.010  4)} = 0.030 M
2
Note that [Na+] = 0.020 M because there are two moles of Na+ per mole of Na2SO4.

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 13
Example: Calculation of Ionic Strength (3 of 4)
Solution
1
(c) μ = {[K + ]  (+1) 2 + [Br − ]  ( −1) 2 + [Na + ]  ( +1) 2 + [SO 24 − ]  ( −2) 2}
2
1
= {(0.020 1) + (0.020 1) + (0.020 1) + (0.010  4)} = 0.050 M
2

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 14
Example: Calculation of Ionic Strength (4 of 4)

Test Yourself: What is the ionic strength of 1 mM CaCl2?

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 15
Charge and Stoichiometry Affect Ionic Strength

Electrolyte Molarity Ionic strength

1: 1 M M
2: 1 M 3M
3: 1 M 6M
2: 2 M 4M

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Box 8-1 Salts with Ions of Charge ≥|2| Do Not Fully
Dissociate

0.025 F NaCl
• [Na+ ] = [Cl− ] = 0.024 9 M
• [NaCl(aq)] = 0.0001 M

0.025 F MgSO4
• [Mg2+ ] = [SO24− ] = 0.016 M
• [MgSO4 (aq)] = 0.009 M

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Box 8-2 Ion Pairing for Single-Cell Analysis

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Section 8-2
Activity Coefficients

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To account for the effect of ionic strength,
concentrations are replaced by activities
Activity ( )
• Value that replaces concentration in a thermodynamically correct
equilibrium expression

Activity coefficient ()

• Measures the deviation of behavior from ideality
• Numeric value used to adjust concentration for ionic strength
• If  = 1, behavior would be ideal
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 20
Reaction: aA + bB cC + dD

• The concentration quotient, 𝐾c , • The correct form of the

did not include activity equilibrium constant, K, accounts
coefficients. (Equation 6-2) for ionic strength. (Equation 8-5)

c d
[C] [D]
Kc = a b
[A] [B]
[C] γ [D] γ c c
C
d d
D
K=
[A]a γ [B]b γ a
A
b
B
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 21
 Consider the Reaction (1 of 2)
CaSO 4 ( s ) Ca 2+ (aq ) + SO 42 − ( aq ) K sp = 2.4×10 −5
From Equation 8-5:

At low ionic strength (μ → 0 M),  Increase ionic strength (↑μ) by adding

approaches unity. a second salt.
• If  = 1, behavior would be ideal. • [Ca2+] and [SO 24 − ] will increase.
• K approaches the concentration • Activity coefficients () must decrease.
quotient.
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 22
Example: Exponents of Activity Coefficients (1 of 3)

Write the solubility product expression for

2−
La 2 (SO 4 )3 ( s) 2La + 3 SO3+
4 with activity coefficients.

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 23
Example: Exponents of Activity Coefficients (2 of 3)

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

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 24
Example: Exponents of Activity Coefficients (3 of 3)

Test Yourself: Write the equilibrium expression for

2+ −
Ca + 2Cl CaCl2 (aq) with activity coefficients.

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 25
Determining Activity Coefficients
Extended Debye-Hückel equation
At moderate ionic strengths
−0.51z 2
μ (0 M    0.1 M), Debye-Hückel
log γ =
1 + α μ / 305 equation works well.
At high ionic strengths
 = activity coefficient
 = ionic strength (0.1 M    2-6 mol/kg), the more
z = ion charge complicated Pitzer equations are
 = ion size (in picometers, pm) used.

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 26
Table 8-1 Activity Coefficients for Aqueous Solutions at 25°C (1 of 4)

Ion size Ionic strength (µ, M)

Ion (𝛼, pm) 0.001 0.005 0.01 0.05 0.1
Charge = ±1
H+ 900 0.967 0.933 0.914 0.86 0.83
(C6 H5 )2 CHCO2− , C3 H7 4 N + 800 0.966 0.931 0.912 0.85 0.82
(O2 N)3 C6 H2 O− , C3 H7 3 NH + , CH3 OC6 H4 CO2− 700 0.965 0.930 0.909 0.845 0.81
Li+, C6 H5 CO− − − −
2 , HOC6 H4 CO2 , ClC6 H4 CO2 , C6 H5 CH2 CO2 ,
+
CH2=CHCH2 CO2− , CH3 2 CHCH2 CO− +
2 , CH3 CH2 4 N , C3 H7 2 NH2 600 0.965 0.929 0.907 0.835 0.80
+
Cl2 CHCO2− , Cl3 CCO− +
2 , CH3 CH2 3 NH , C3 H7 NH3 500 0.964 0.928 0.904 0.83 0.79
Na+ , CdCl+ , ClO− − − − − −
2 , IO3 , HCO3 , H2 PO4 , HSO3 , H2 AsO4 ,
Co NH3 4 NO2 + − −
2 , CH3 CO2 , ClCH2 CO2 , CH3 4 N ,
+

CH3 CH2 2 NH2+ , H2 NCH2 CO− 2 450 0.964 0.928 0.902 0.82 0.775

All ions of the same size and charge appear in the same group and have the same .
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Table 8-1 Activity Coefficients for Aqueous Solutions at 25°C (2 of 4)

Ion size Ionic strength (µ, M)

Ion (𝛼, pm) 0.001 0.005 0.01 0.05 0.1
Charge = ±1
+
H3 NCH2 CO2 H, CH3 3 NH + , CH3 CH2 NH3+ 400 0.964 0.927 0.901 0.815 0.77
OH − , F −, SCN − , OCN − , HS− , ClO− − − − −
3 , ClO4 , BrO3 , IO4 , MnO4 ,
+ +
HCO− −
2 , H2 citrate , CH3 NH3 , CH3 2 NH2 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+ , Ti+ , Ag + 250 0.964 0.924 0.898 0.80 0.75

Note: Ion sizes are empirical parameters.

• Sizes cannot be taken literally. However, trends are sensible.
• Small highly charged ions bind solvent more tightly and have larger effective radius.

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 28
Table 8-1 Activity Coefficients for Aqueous Solutions at 25°C (3 of 4)

Ion size Ionic strength (µ, M)

Ion (𝛼, pm) 0.001 0.005 0.01 0.05 0.1
Charge = ±2
Mg 2+ , Be2+ 800 0.872 0.755 0.69 0.52 0.45
CH2 CH2 CH2 CO− −
2 2 , CH2 CH2 CH2 CO2 2 700 0.872 0.755 0.685 0.50 0.425
Ca2+ , Cu2+ , Zn2+, Sn2+, Mn2+, Fe2+, Ni2+ , Co2+, C6 H4 CO−
2 2,
H2 C CH2 CO− −
2 2 , CH2 CH2 CO2 2 600 0.870 0.749 0.675 0.485 0.405
Sr 2+ , Ba2+ , Cd2+ , Hg 2+ , S2− , S2 O2− 2− −
4 , WO4 , H2 C CO2 2 ,
CH2 CO− 2 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 5 Cl , Fe CN 5 NO ,
C2 O2−
4 , Hcitrate
2− 450 0.867 0.742 0.665 0.455 0.37
Hg 2+ 2− 2− 2− 2− 2− 2− 2−
2 , SO4 , S2 O3 , S2 O6 , S2 O8 , SeO4 , CrO4 , HPO4 400 0.867 0.740 0.660 0.445 0.355

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Table 8-1 Activity Coefficients for Aqueous Solutions at 25°C (4 of 4)

Ion size Ionic strength (µ, M)

Ion (𝛼, pm) 0.001 0.005 0.01 0.05 0.1
Charge = ±3
Al3+ , Fe3+, Cr 3+ , Sc 3+, Y 3+, In3+, lanthanides 𝑎 900 0.738 0.54 0.445 0.245 0.18
citrate3− 500 0.728 0.51 0.405 0.18 0.115
PO3−
4 , Fe CN
3−
6 , Cr NH3 3+
6 , Co NH3 3+
6 , Co NH3 5 H2 O3+ 400 0.725 0.505 0.395 0.16 0.095
Charge = ±4
Th4+ , Zr 4+ , Ce4+ , Sn4+ 1 100 0.588 0.35 0.255 0.10 0.065
4−
Fe CN 6 500 0.57 0.31 0.20 0.048 0.021
a. Lanthanides are elements 57–71 in the periodic table.

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 As Ionic Strength Increases from 0 to 0.1 M
Figure 8-4
• As ionic strength increases, activity coefficient
decreases.
• Activity coefficient () approaches unity as ionic
strength () approaches 0.
• As magnitude of the charge (z) of the ion increases,
activity coefficient () deviates from unity.
• Activity corrections are more important for ions
with charge of 3 than charge of 1.
• The smaller the ion size (), the more important
activity effects become.
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 31
Example: Using Table 8-1 (1 of 3)
Find the activity coefficient of Ca2+ in a solution of 3.3 mM CaCl2.

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 32
 Example: Using Table 8-1 (2 of 3)
Solution
The ionic strength is
1
 = {[Ca 2+ ]  22 + [Cl− ]  ( −1) 2 }
2
1
= {(0.003 3)  4 + (0.006 6) 1} = 0.010 M
2
In Table 8-1, Ca2+ is listed under the charge ±2 and has a size of 600 pm.
Thus  = 0.675 when μ = 0.010 M.

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 33
Example: Using Table 8-1 (3 of 3)
Test Yourself: Find 𝛾 for Cl− in 0.33 mM CaCl2.

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 34
 Interpolating Activity Coefficients
Linear interpolation Unknown y interval known x interval
=
Δy Δx
• Assume the values between two
neighboring entries of a table can
be approximated by a straight line. Do not confuse two terms:
• Fast alternative to the Debye- • Interpolation estimates a number
between two values on a table.
Hückel equation when calculating
• Extrapolation estimates a number that
activity coefficients. lies beyond the values on a table.

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 35
 Interpolating Activity Coefficients Using Table 8.1
Linear interpolation is a simple ratio:

Unknown y interval known x interval

• x = 16 is 60% of the way from 10 to 20. =
Δy Δx
• Therefore, the corresponding y-value will be
60% of the way from 0.67 to 0.83. 0.83 − y 20 − 16
=  y = 0.766
0.83 − 0.67 20 − 10
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 36
Example: Interpolating Activity Coefficients (1 of 4)

Calculate the activity coefficient of H+ when μ = 0.025 M.

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 Example: Interpolating Activity Coefficients (2 of 4)
Solution µ 𝛾 for H+
0.01 0.914
H+ is the first entry in Table 8-1.
0.025 ?
The linear interpolation is set up as follows: 0.05 0.86

Unknown  interval known  interval

=
 
0.86 −  0.05 − 0.025
=
0.86 − 0.914 0.05 − 0.01
 = 0.894
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 38
Example: Interpolating Activity Coefficients (3 of 4)

Another Solution
A better, but slightly more tedious, calculation uses Equation 8-6, with
the ion size α = 900 pm listed for H+ in Table 8-1:

(−0.51)(12 ) 0.025
log  H+ = = −0.05498
1 + (900 0.025 / 305)
−0.054 98
 H+ = 10 = 0.881

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 39
Example: Interpolating Activity Coefficients (4 of 4)

Test Yourself: By interpolation, find 𝛾 for H+ when μ = 0.06 M.

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 40
 Activity Coefficients of Nonionic Compounds
Neutral molecules have an activity coefficient   1 (when  < 0.1 M).
• Activity  concentration for neutral species

Gases have an activity coefficient   1 (when pressure < 1 bar).

• Activity  pressure of the gas

• Note: fugacity = the activity of a gas

• Deviation from ideal gas behavior is fugacity coefficient
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Activity Coefficients at High Ionic Strength
At high ionic strengths,   1 M. Figure 8-5
• Activity coefficients deviate from trends
observed on Table 8-1.
•  increases with increasing .

Figure 8-5:
in NaClO4 solutions of high ionic strength.
• Behavior differs from dilute aqueous solutions.
• Solvent is no longer pure H2O, but a mixture of H2O
and salt.

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 42
Example: Using Activity Coefficients (1 of 3)
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.

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 43
Example: Using Activity Coefficients (2 of 3)
Solution
We find [Ca2+] from the solubility product expression, including
activity coefficients. The ionic strength of 0.050 M NaF is 0.050 M. At
μ = 0.050 0 M in Table 8-1, we find  Ca = 0.485 and  F = 0.81. 2+ −

K sp = [Ca 2+ ] Ca 2+ [F− ]2  F2 −
3.2 10−11 = [Ca 2+ ](0.485)(0.050) 2 (0.81) 2
[Ca 2+ ] = 4.0 10−8 M

The value of Ksp came from Appendix F. Note that  F− is squared.

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 44
Example: Using Activity Coefficients (3 of 3)
Test Yourself: Find [Hg 22+ ] in equilibrium with 0.010 M KCl saturated with
Hg2Cl2.

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 45
Section 8-3
pH Revisited

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 46
pH Revisited

Activities can be used to calculate a more accurate value for pH.

• The definition becomes pH  − log[H + ]

• When a pH meter is used to measure pH, we are attempting to measure

the negative logarithm of hydrogen ion activity, not concentration.

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 47
Example: pH of Pure Water at 25°C (1 of 3)
Let’s calculate the pH of pure water by using activity coefficients.

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 48
Example: pH of Pure Water at 25°C (2 of 3)
Solution
The relevant equilibrium is

H 2O H + + OH − (8-9)

(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
K W = 1.0 10−14 = ( x)  H+ ( x)  OH−
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Example: pH of Pure Water at 25°C (3 of 3)
Solution
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 10−14 = ( x)(1)( x)(1) = x 2  x = 1.0 10−7 M

The concentrations of H+ and OH− are both 1.0 × 10−7 M. The ionic strength
is 1.0 × 10−7 M, so each activity coefficient is very close to 1.00. The pH is
+ −7
pH = − log[H ] H+ = − log(1.0 10 )(1.00) = 7.00

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 50
Example: pH of Water Containing a Salt (1 of 4)

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

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 51
Example: pH of Water Containing a Salt (2 of 4)

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 μ = 0.10 M. Putting these values
into Equation 8-10 gives
K W = [H + ] H+ [OH − ] OH−
1.0 10−14 = ( x)(0.83)( x)(0.76)
x = 1.26 10−7 M

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 52
 Example: pH of Water Containing a Salt (3 of 4)

Solution
The concentrations of H+ and OH− are equal and are both greater than
1.0 × 10−7 M. The activities of H+ and OH− are not equal in this solution:

Finally, we calculate

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 53
Example: pH of Water Containing a Salt (4 of 4)

Test Yourself: Find [H+] and the pH of 0.05 M LiNO3.

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 54
 Comparing Values Calculated
with and Without Activities
• The pH of pure water at 25C • The pH of water containing a
salt (0.10 M KCl) at 25C
pH = 7.00
pH = 6.98
[H+] = 1 × 10−7 M
[H+] = 1.26 × 10−7 M

This may seem like a small difference (0.02 pH units) but this
corresponds to a concentration change of 26% [H+].

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 55
Section 8-4
Systematic Treatment of Equilibrium

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 Systematic Treatment of Equilibrium
The systematic treatment of equilibrium is a way to deal with all types of
chemical equilibria, regardless of their complexity.
• Set up general equations.
• Introduce specific conditions and/or reasonable approximations.
• If simplification calculations are difficult, use spreadsheets for numerical
solutions.
Key to procedure is to write as many independent algebraic equations as
there are unknown species in the system.
• Chemical equilibrium
• Charge balance
• Mass balance
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 57
 Charge Balance
Charge balance (Equation 8-12)
• Algebraic statement of electroneutrality
• Sum of positive charges in solution = sum of negative charges in solution
• Solutions must have zero total charge

Note: Activity coefficients do not appear in the charge balance.

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 58
 Consider a 1.00-L Solution Containing 0.0250 mol
of KH2PO4 + 0.0300 mol of KOH
Figure 8-6
Concentrations of all species at equilibrium are
[H+ ] = 3.9 ×10 −12 M [H2PO4− ] = 1.4 ×10 −6 M
+ 2−
[K ] = 0.055 50 M [HPO4 ] = 0.022 56 M
[OH− ] = 0.002 56 M [PO34− ] = 0.002 44 M
Are the charges balanced?

H+ + K + = OH− + H2 PO−
4 + 2 HPO 2−
4 + 3[PO 3−
4 ]

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 59
Example: Writing a Charge Balance (1 of 3)
Write the charge balance for a solution containing H2O, H+, OH−,
ClO4− , Fe(CN)63− , CN− , Fe3+ , Mg 2+ , CH3OH, HCN, NH3 , and NH+4 .

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 60
Example: Writing a Charge Balance (2 of 3)
Solution
Neutral species (H2O, CH3OH, HCN, and NH3 ) contribute no charge, so the
charge balance is

[H+ ]+ 3[Fe3+ ]+ 2[Mg 2+ ]+[NH+4 ] = [OH− ]+[ClO 4− ]+ 3[Fe(CN)36− ]+[CN− ]

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 61
Example: Writing a Charge Balance (3 of 3)
Test Yourself: What would be the charge balance if you add MgCl2 to
the solution and it dissociates int Mg2+ + 2Cl−?

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 62
 Mass Balance
Mass balance (or material balance)
• Conservation of matter
o Refers to conservation of atoms, not mass
• Quantity of all species containing a particular atom (or group of atoms)
must be equal to the amount of that atom (or group) initially delivered to
solution
Formal concentration =  all relevant species after reaching equilibrium
i

Note: Activity coefficients do not appear in the mass balance.

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 63
Consider the Reaction (2 of 2)

CH 3CO 2 H CH 3CO 2− + H + K a = 1.75×10−5

Mass balance at equilibrium:

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 64
Example: Mass Balance When the Total
Concentration Is Known (1 of 3)
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.

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 65
Example: Mass Balance When the Total
Concentration Is Known (2 of 3)
Solution
All K+ present in solution came from the dissociation of the two salts.
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 ]+[H2PO4− ]+[HPO24− ][PO34− ] = 0.025 0 M

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 66
Example: Mass Balance When the Total
Concentration Is Known (3 of 3)
Test Yourself: Write two mass balances for a 1.00-L solution containing
0.100 mol of sodium acetate.

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 67
 Consider the reaction
La(IO3 )3 (s) La3+ (aq) + 3IO3− (aq)
[Total iodate] = 3[total lanthanum]
• Extent of dissociation is not known.
↓
• Ratio of dissociated species is known.
[IO −3 ] = 3[La 3+ ]
[IO −3 ] must be 3× greater than [La 3+ ]

If solution also contains the ion pair LaIO32+ and the hydrolysis product LaOH2+
[Total iodate] = 3[total lanthanum]
[IO −3 ] +[LaIO 32+ ] = 3([La 3+ ] +[LaIO 2+
3 ] +[LaOH 2+
])

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 68
Example: Mass Balance When the Total
Concentration Is Unknown (1 of 3)
Write the mass balance for a saturated solution of the slightly soluble
salt Ag3PO4, which produces PO34− and 3Ag + when it dissolves.

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 69
 Example: Mass Balance When the Total
Concentration Is Unknown (2 of 3)
Solution
If the phosphate in solution remained as PO34− , we could write
[Ag + ] = 3[PO34− ]
because three silver ions are produced for each phosphate ion. However, phosphate
reacts with water to give HPO 24− , H 2 PO 4− , and H 3PO 4 , so the mass balance is

[Ag + ] = 3{[PO34− ] + [HPO 42− ] + [H 2 PO 4− ] + [H 3PO 4 ]}

That is, the number of atoms of Ag + must equal three times the total number of
atoms of phosphorus, regardless of how many species contain phosphorus.

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 70
 Example: Mass Balance When the Total
Concentration Is Unknown (3 of 3)
Test Yourself: Write the mass balance for a saturated solution of
Ba(HSO4)2 if the species in solution are Ba2+ , BaSO4 (aq), HSO4− , SO24− , and BaOH+ .

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 71
 Box 8-3 Calcium Carbonate Mass Balance in Rivers
Dissolution of calcite is the most common
source of Ca2+ in rivers and lakes.
CaCO 3 ( s )+ CO 2 (aq ) + H 2O( l ) Ca 2+ (aq ) + 2HCO −3 (aq )
Calcite Bicarbonate

Near pH = 7, bicarbonate is primary product and

2[Ca 2+ ]  [HCO −3 ]

• Rivers along the line have water saturated with CaCO3.

• Rivers above the line contain a high concentration of
dissolved CO2. This shifts the equilibrium and the
mass balance ratio.
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 72
Section 8-5
Applying the Systematic Treatment
of Equilibrium

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 73
A Systematic Approach to Solving Complex
Equilibria (1 of 2)
1. Write the pertinent reactions. (balanced chemical reactions)
2. Write the charge balance equation. (if possible)
3. Write mass balance equations. (There may be more than one.)
4. Write the equilibrium constant expressions for each chemical reaction
listed in step 1. (Note: Use activities here.)
5. Count the equations and unknowns. (If # equations = # unknown chemical
species, there is enough information to solve.)
Note: If #EQ ≠ #UNK, then (a) you have overlooked an equilibrium reaction or (b)
you will need to estimate some concentrations.
6. Solve for all the unknown chemical species.
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 74
A Systematic Approach to Solving Complex
Equilibria (2 of 2)
Steps 1 and 6 are the heart of the problem.
• Guessing which chemical equilibria exist in a solution requires chemical intuition and
practice.
• Identifying all chemical reactions can be difficult, so undoubtedly many equilibrium
problems get oversimplified.

With n equations and n unknowns, the problem CAN be solved (in principle).
• Simple cases can be solved by hand.
• More complex problems require approximations and spreadsheets.

Always pay attention.

• Does the problem require you to solve for all chemical species in solution or just some?
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 75
Find the Concentrations of All Species in an Aqueous
Solution Containing 0.010 0 mol NH3 in 1.000 L (1 of 2)
Step 1: pertinent reactions
NH 3 + H 2 O NH +4 + OH − K b = 1.76 10−5
H 2O H + + OH − K W = 1.00 10−14
Step 2: charge balance
[NH +4 ] + [H + ] = [OH − ] Step 4: equilibrium expressions
Step 3: mass balance
[NH +4 ] NH+ [OH − ] OH−
[NH 3 ] + [NH +4 ] = 0.010 0 M  F Kb = 4

[NH 3 ] NH 3
Step 5: count K W = [H + ] H+ [OH − ] OH−
4 equations: Kb, Kw, C.B., M.B. Step 6: solve
4 unknowns: [NH3 ], [NH 4 + ], [H + ], [OH − ]
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 76
 Find the Concentrations of All Species in an Aqueous
Solution Containing 0.010 0 mol NH3 in 1.000 L (2 of 2)
Solving this “simple” problem is complicated. • Rearrange Kw expression:
To start: [OH − ] = K w /[H + ]
• Ignore activity coefficients.
• Substitute [OH−] into C.B. and rearrange for [NH 4 + ] :
• Eliminate one variable at a time until
single unknown is left. [NH +4 ] + [H + ] = K w / [H + ]
• Since acid-base problem, start by [NH +4 ] = K w /[H + ] − [H + ]
expressing as much as possible in terms of
• Substitute [NH 4 + ] into M.B. and rearrange for [NH3]:
[H+].
➢ Substitute 3 new equations into Kb [NH 3 ] + K w /[H + ] − [H + ] = F
expression: [NH 3 ] = F− K w /[H + ] + [H + ]
[NH +4 ][OH − ] ( K w /[H + ] − [H + ])( K w /[H + ]) Looks complex but [H+] is only unknown.
Kb = =
[NH 3 ] F − K w /[H + ] + [H + ] Everything else is a constant.
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 77
 + − + + +
[NH ][OH ] ( K w / [H ] − [H ])( K w /[H ])
Solve: Kb = = 4
+ +
(8-21)
[NH 3 ] F − K w / [H ] + [H ]
Figure 8-7
Equation 8-21 only contains one
variable, [H+], but solving can be
nontrivial.
Excel has a built-in procedure
called Goal Seek that solves
equations with one unknown.
The spreadsheet in Figure 8-7
contains all the relevant
information.
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 78
Goal Seek (Solving Equations with One Unknown)
• Adjust pH (cell B7) until difference in cell B13 is close to zero.
• Apply Goal Seek in Excel.
• See textbook for other simplifying approximations.
Figure 8-8

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 79
 Solubility and Hydrolysis of Thallium(I) Azide (1 of 2)

Step 1: pertinent reactions

TIN 3 ( s) Tl+ (aq) + N 3− (aq) K sp = 10−3.66
N 3− + H 2 O NH 3 + OH − K b = 10−9.35
H 2O H + + OH − K w = 10−14.00

Step 2: charge balance

[Tl+ ] + [H + ] = [N 3− ] + [OH − ]
Step 3: mass balance
[Tl+ ] = [N 3− ] + [NH 3 ]

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 80
 Solubility and Hydrolysis of Thallium(I) Azide (2 of 2)
Step 4: equilibrium expressions
K sp = [Tl+ ] Tl+ [N 3− ] N− = 10−3.66
3

[HN 3 ] HN3 [OH − ] OH−

Kb = = 10−9.35
[N 3− ] N−
3

K w = [H + ] H+ [OH − ] OH− = 10−14.00

Step 5: count
5 equations: Ksp, Kb, Kw, C.B., M.B.
5 unknowns: [Tl+ ], [N 3− ], [HN 3 ], [H + ], [OH − ]
Step 6: solve Use a spreadsheet and ignore activity coefficients.
Number of concentrations to estimate = (number of unknowns) − (number of equilibria)
=5−3=2
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 81
Figure 8-9 Thallium(I) Azide Solubility Spreadsheet

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 82
Figure 8-10 Solver Parameters and Solver Options

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 83
Figure 8-11 Thallium(I) Azide Solubility Spreadsheet

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 84
Solubility of Magnesium Hydroxide with Activity
Coefficients (1 of 2)
Step 1: pertinent reactions
Mg(OH) 2 ( s) Mg 2+ (aq) + 2 OH − ( aq) K sp = 10−11.15
Mg 2+ + OH − MgOH + K1 = 1 = 102.6
H 2O H + + OH − K w = 10−14.00
Step 2: charge balance
2[Mg 2+ ] + [MgOH + ] + [H + ] = [OH − ]
Step 3: mass balance
2[Mg 2+ ] + [MgOH + ] + [H + ] = [OH − ] (equivalent to charge balance)

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 85
 Solubility of Magnesium Hydroxide with Activity
Coefficients (2 of 2)
Step 4: equilibrium expressions
K sp = [Mg 2+ ] Mg2+ [OH − ]2  OH
2
− = 10
−11.15

[MgOH + ] MgOH+
K1 = = 102.6
[Mg 2+ ] Mg2+ [OH − ] OH−
K w = [H + ] H+ [H − ] OH− = 10−14.00
Step 5: count
4 equations: Ksp, K1, Kw, C.B./M.B.
4 unknowns: [Mg 2+ ], [Mg OH + ], [H + ], [OH − ]
Step 6: solve Use a spreadsheet and include activity coefficients.
Number of concentrations to estimate = (number of unknowns) − (number of equilibria)
=4−3=1
Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 86
Figure 8-12 Magnesium Hydroxide Solubility Spreadsheet

Quantitative Chemical Analysis, Daniel C. Harris and Charles A. Lucy, © 2020 W. H. Freeman and Company 87