Complex Equilibrium

System
Example 7-5
Calculate the molar solubility of Mg(OH)2 in
water.
 Step I: Pertinent Equilibria,
 Mg(OH)2(s)  Mg2+ + 2OH-
 2H2O  H3O+ + OH-
 Step 2: Definition of Unknown
 Since 1 mol of Mg2+ is formed for each
mole of Mg(OH)2 dissolved,
 solubility Mg(OH)2 = [Mg2+]
 Step 3: Equilibrium-Constant Expressions
 Ksp = [Mg2+][OH-]2 = 7.1 × 10-12
 Kw = [H3O+][OH-] = 1.00 × 10-14
 Step 4: Mass-Balance Expression
 [OH-] = 2[Mg2+] + [H3O+]
 The first term on the right-hand side of equation
represents the hydroxide ion concentration resulting
from dissolved Mg(OH)2 in the solution, and the
second term is the hydroxide ion concentration
resulting from the dissociation of water.
 Step 5: Charge-Balance Expression
 [OH-] = 2[Mg2+] + [H3O+]
 Often a mass-balance and a charge-balance
equation are the same.
 Step 6: Number of Independent Equations and
Unknowns
 three unknowns ([Mg2+], [OH-], and [H3O+]).
 Therefore, the problem can be solved
rigorously.
 Step 7: Approximations
 Since the solubility-product constant for Mg(OH)2 is
relatively large, the solution will be somewhat basic.
Therefore, it is reasonable to assume that [H3O+] <<
[Mg2+]. Equation 7-7 then simplifies to
 2[Mg2+] = [OH-]
 Step 8: Solution to Equations
 Substitution of Equation 7-8 into Equation 7-5 gives
 [Mg2+](2[Mg2+])2 = 7.1 × 10-12
 [Mg2+]3 = 7.1 × 10-12/4 = 1.78 × 10-12
 [Mg2+] = solubility = 1.21 × 10-4 = 1.2 × 10-4 mol/L
 Step 9: Check of the Assumptions
 Substitution into Equation 7-8 yields
 [OH-] = 2 × 1.21 × 10-4 = 2.42 × 10-4
 Thus our assumption that 4.1 × 10-11 <<
1.2 × 10-4 is valid.
Example 7-6
Calculate the solubility of Fe(OH)3 in water.
 Proceeding by the systematic approach used
in Example 7-5 gives
 Step 1: Pertinent Equilibrium
 Fe(OH)3(s)  Fe3+ + 30H-
 2H2O  H3O+ + OH-
 Step2: Definition of Unknown
 solubility = [Fe3+]
 Step 3: Equilibrium-Constant Expressions
 Ksp= [Fe3+][OH-]3 = 2 × 10-39
 Kw = [H3O+][OH-] = 1.00 × 10-14
 Steps 4 and 5
 As in Example 7-5, the mass-balance
equation and the charge-balance equations
are identical. That is.
 [OH-] = 3[Fe3+] + [H3O+].
 Step 6
 We see that we have enough equations to calculate
values for the three unknowns
 Step 7: Approximations
 As in Example 7-5. let us assume
 [H3O+] << 3[Fe3+], so that
 3[Fe3+] = [OH-]
 Step 8: Solution to Equations
 Substituting this equation into the solubility-product
expression gives .
Check the Assumption
 [Fe3+](3[Fe3+])3 = 2 X 10-39
 [Fe3+] = 9 × 10-11
 solubility = [Fe3+] = 9 × 10-11 mol/L
 Step 9: Check or the Assumptions
 From the assumption made in step 7, we can
calculate a provisional value of [OH-]. That is,
 [OH-] = 3[Fe3+] = 3 × 9 × 10-11 = 3 × 10-10
New Assumption
 Let us use this value of [OH-] to compute a
provisional value for [H3O+]:
 [H3O+] = 1.00 × 10-14/3 × 10-10 = 3 × 10-5
 But 3 X 10-5 is not much smaller than three times our
provisional value of [Fe3+]. This discrepancy means
that our assumption was invalid and the provisional
values for [Fe3+], [OH-], and [H3O+] are all significantly
in error. Therefore. Let us go back to step 7 and
assume that
 3[Fe3+] << [H3O+]
Revised Asummption
 Now the mass-balance expression becomes
 [H3O+] = [OH-]
 Substituting this equality into the expression for Kw
gives [H3O+] = [OH-] = 1.00 X 10-7
 Substituting this number into the solubility-product
expression developed in step 3 gives
 [Fe3+] = 2 × 10-39/(1.00 × 10-7)3 =2 × 10-18 mol/L
 In this case we have assumed that 3[Fe3+] << [OH-]
or 3 x 2 x 10-18 << 10-7. Thus our assumption is valid
and we may write
 solubility = 2 × 10-18 mol/L
Detection of Invalid Assumption
 Example 7-6 illustrates how easily the effects of an
invalid assumption are detected.
 You may be bothered that we used a faulty value for
[OH-] to obtain [H3O+], which we then compared with
3[Fe3+].
 But the point is, that the faulty value of [OH-] also
resulted from invalid assumption.
 Had the assumption been valid we would have had
an internally consistent set of calculated
concentrations.
 The presence of even one internal inconsistency is a
clear indication of an invalid assumption.
 A valid assumption leads to concentrations that
satisfy all of the algebraic equations written in steps
3, 4, and 5.
7B-2 The Effect of pH on Solubility

 The solubility of precipitates containing an

anion with basic properties, a cation with
acidic properties. or both will be dependent
on pH. The example that follows illustrates
how the effect of pH on solubility can be
treated in quantitative terms.
Solubility Calculations When the pH
Is Fixed and Known
 Analytical precipitations are frequently
performed in buffered solutions in which the
pH is fixed at some predetermined and
known value.
All precipitates that contain an anion that is
the conjugate base of a weak acid are more
soluble at low pH than at high pH.
 A buffer keeps the pH of a solution constant
Example 7-7
 Calculate the molar solubility of calcium
oxalate in a solution that has been buffered
so that its pH is constant and equal to 4.00.
Solution steps:
 Step I: Pertinent Equilibria
 CaC2O4  Ca2+ + C2O42- (7-9)
 Oxalate ions react with water to form HC2O4-
and H2C2O4. Thus, two other equilibria in this
solution are
 H2C2O4 + H2O  H3O+ + HC2O4-
 HC2O4- + H2O  H3O+ + C2042-
Step 2: Definition of the unknown

 Calcium oxalate is a strong electrolyte so that

its molar analytical concentration is equal to
the equilibrium calcium ion concentration.
That is,
 Solubility = [Ca2+]
Step 3: Equilibrium-Constant Expressions

 Ksp = [Ca2+][C2O42-]
 K1= [H3O+][HC2O4-]/[ H2C2O4]
 K2= [H3O+][C2O42-]/[ HC2O4-]
 Step 4: Mass-Balance Expressions
 Because CaC2O4 is the only source of Ca2+
and the three oxalate species,
 [Ca2+] = [C2O4-] + [HC2O4] + [H2C2O4]
 Moreover, the problem states that the pH is
4.00. Thus,
 [H3O+] = 1.00 × 10-4
Step 5: Charge-Balance Expression

 A buffer is required to maintain the pH

at 4.00. The buffer usually consists of
some weak acid HA and its conjugate
base, A- (Section 10C-1 ). The nature
of the three species and their
concentrations have not been
specified, however, So we do not have
enough information to write a charge-
balance equation.
Step 6: Number of Independent
Equations and Unknowns

 We have four unknowns ([Ca2+],

[C2O42-], [HC2O4-], and [H2C2O4]) as
well as four independent algebraic
relationships (Equations 7-13,7-
14,7-15, and 7-16). Therefore, an
exact solution can be obtained, and
the problem becomes one of
algebra.
Step 8: Solution of the Equations
 Step 7: Approximations
 We can easily obtain an exact solution in this case,
So we will not bother with approximations.
 Let us substitute Equations 7-14 and 7-15 into 7-16
to develop a relationship between [Ca2+], [C2O42-],
and [H3O+]. Thus, we rearrange Equation 7-15 to
give
 [HC2O42-] = [H3O+][C2O42-]/K2
 Substituting numerical values for [H3O+] and K2 gives
 [HC2O4-] = 1.00 × 10-4 [C2O42-]/5.42 × 10-5 = 1.85
[C2O42-]
Calculation:
 Substituting numerical values for [H3O+] and
K1 yield
 [H2C2O4] = 1.85 × 10-4 [C2O42-]/5.60 × 10-2 =
3.30 × 10-3 [C2O42-]
 Substituting these expressions for [HC2O4-]
and [H2C2O4] into Equation 7-16 gives
 [Ca2+] = [C2O42-] + 1.85 [C2O42-] + 3.30 × 10-3
[Ca2+] = 2.85 [C2O42-]
 or [C2O42-] = [Ca2+]/2.85
Final result:
 Substituting into Equation 7-13 gives
 [Ca2+][Ca2+]/2.85=1.7 × 10-9
 [Ca2+] = solubility = 2.85 × 1.7 X 10-9 = 7.0 ×
10-5 mol/L.
Solubility Calculations When the pH Is
Variable
 Saturating an unbuffered solution with a
sparingly soluble salt containing a basic
anion or an acidic cation causes the pH of
the solution to change. For example, pure
water saturated with barium carbonate is
basic as a consequence of the reactions
 BaCO3(s)  Ba2+ + CO32-
 CO32- + H2O  HCO3- + OH-
 HCO3- + H2O  H2CO3 + OH-
Variable pH
 In contrast to Example 7-6, the hydroxide ion
concentration now becomes an unknown,
and an additional algebraic equation must
therefore be developed if the solubility of
barium carbonate is to be calculated.
 It is not difficult to write the algebraic
relationships we need to calculate the
solubility of such a precipitate. Solving the
equations exactly, however, is tedious unless
appropriate software is available.
The Solubility of Precipitates in the
Presence of Complexing Agents
 The solubility of a precipitate may increase
dramatically in the presence of reagents that
form complexes with the anion or the cation
of the precipitate. For example, fluoride ions
prevent the quantitative precipitation of
aluminum hydroxide even though the
solubility product of this precipitate is
remarkably small (3 × 10-34).
Fluoride Complex
 The cause of the increase in solubility is
shown by the equations
 Al(OH)3(s)  Al3+ + 3 OH-
 Al3++ 6F-  AlF63-
 The fluoride complex is sufficiently stable to
permit fluoride ions to compete successfully
with hydroxide ions for aluminum ions.
Complex Formation with an Ion That Is
Common to the Precipitate
 Many precipitates react with the precipitating
reagent to form soluble complexes.
 In a gravimetric analysis. this tendency may
have the unfortunate effect of reducing the
recovery of analytes if too large an excess of
reagent is used.
 For example, in solutions containing high
concentrations of chloride, silver chloride
forms chloro complexes such as AgCl2- and
AgCl32- .
Complex and solubility
 The effect of these complexes is illustrated in Figure
7-2, in which the experimentally determined solubility
of silver chloride is plotted against the logarithm of
the potassium chloride concentration.
 For low anion concentrations, the experimental
solubilities do not differ greatly from those calculated
with the solubility-product constant for silver chloride;
beyond a chloride ion concentration of about 10-3 M,
however, the calculated solubilities approach zero
while the measured values rise steeply.
 Note that the solubility of silver chloride is about the
same in 0.3 M KCl as in pure water, and is about
eight times that figure in a 1 M solution.
 We can describe these effects quantitatively if the
compositions of the complexes and their formation
constants are known.
Hydroxide Complex
 Increases in solubility caused by large excesses of a
common ion are not unusual. Of particular interest
are amphoteric hydroxides, which are sparingly
soluble in dilute base but are redissolved by excess
hydroxide ion.
 The hydroxides of zinc and aluminum, for example,
are converted to the soluble zincate and aluminate
ions upon treatment with excess base. For zinc, the
equilibria can be represented as
 Zn2+ + 2OH-  Zn(OH)2(s)
 Zn(OH)2(s) + 2OH-  Zn(OH)42-
 As with silver chloride. the solubilities of
amphoteric hydroxides pass through minima
and then increase rapidly with increasing
concentrations of base.
 The hydroxide ion concentration at which the
solubility is a minimum can be calculated.
Provided equilibrium constants for the
reactions are available.
Quantitative Treatment of the Effect of
Complex Formation on Solubility.

 Solubility calculations for a precipitate in the

presence of a complexing reagent are similar
in principle to those discussed in the
previous section. Formation constants for the
complexes involved must be available.
SEPARATION OF IONS BASED ON SOLUBILITY
DIFFERENCES; SULFIDE SEPARATIONS

 Several precipitating agents permit separation of

ions based on solubility differences. Such
separations require close control of the active
reagent concentration at a suitable and
predetermined level.
 Most often, such control is achieved by controlling
the pH of the solution with suitable buffers.
 This technique is applicable to anionic reagents in
which the anion is the conjugate base of a weak
acid.
 Examples include sulfide ion (the conjugate base of
hydrogen sulfide), hydroxide ion (the conjugate base
of later), and the anions of several organic weak
acids.
Precipitation of Sulfides
 Sulfide ion forms precipitates with heavy-metal
cations that have solubility products ranging from 10-
10 to 10-50 or smaller.

 In addition, the concentration of S2- can be varied

over a range of about 0.1 M to 10-22 M by controlling
the pH of a saturated solution of hydrogen sulfide.
 These two properties make possible a number of
useful cation separations.
 To illustrate the use of hydrogen sulfide to separate
cations based on pH control, let us consider the
precipitation of the divalent cation M2+ from a
solution that is kept saturated with hydrogen sulfide
by bubbling the gas continuously through the
solution.
The important equilibria in this solution are:

 MS(s)  M2+ + S2-

 Ksp = [M2+][S2-]
 H2S + H2O  H3O+ + HS-
 K1=[H3O+][HS-]/[H2S] = 9.6 × 10-8
 HS- + H2O  H3O+ +S2-
 K2=[H3O+][S2-]/[HS-] = 1.3 × 10-14
solubility:
 We may also write
 Solubility = [M2+]
 The concentration of hydrogen
sulfide in a saturated solution of the
gas is approximately 0.1 M. Thus,
we may write as a mass-balance
expression
 [S2-] + [HS-] + [H2S] = 0.1
Assumption:
 Because we know the hydronium ion
concentration, we have four unknowns,
the concentration of the metal ion and
the three sulfide species.
 We can simplify the calculation greatly
by assuming that:
 ([S2-] + [HS-]) << [H2S] so that
 [H2S] = 0.10 mol/L
expression for the overall dissociation of
hydrogen sulfide to sulfide ion
 H2S + 2H2O  2H3O+ + S2-
 K1K2 = [H3O+]2[S2-]/ [H2S] = 1.2 × 10-21
 The constant for this overall reaction is simply
the product of K1 and K2. Substituting the
numerical value for [H2S] into this equation
gives
 [H3O+]2[S2-]/0.10 = 1.2 × 10-21
 On rearranging this equation, we obtain
 [S2-]= 1,2 × 10-22/[H3O+]2
Control of pH
 Thus, we see that the sulfide ion
concentration of a saturated hydrogen sulfide
solution varies inversely as the square of the
hydrogen ion concentration.
 Figure 7-3, which was obtained with this
equation reveals that the sulfide ion
concentration of an aqueous solution can be
varied by over 20 orders of magnitude within
the pH range from 1 to 11.
Equation for Solubility:
 Substituting Equation 7-23 into the solubility-
product expression gives
 Ksp = [M2+] × 1.2 × 10-22/[H3O+]2
 Solubility = [M2+] = [H3O+]2 Ksp/1.2 × 10-22
 Thus, the solubility of a divalent metal sulfide
increases as the square of the hydronium ion
concentration.
Example 7-8

 Cadmium sulfide is less soluble than

thallium(I) sulfide. Find the conditions under
which Cd2+ and TI+ can; in theory, be
separated quantitatively with H2S from a
solution that is 0.1 M in each cation.
The constants for the two solubility
equilibria are:
 CdS(s) === Cd2+ + S2-
 Ksp = [Cd2+][S2-] = 1 × 10-27
 Tl2S(s) === 2Tl- + S2-
 Ksp = [Tl-]2[S2-] = 6 × 10-22
 Since CdS precipitates at a lower [S2-] than
does TI2S, we first compute the sulfide ion
concentration necessity for quantitative
removal of Cd2+ from solution
a quantitative removal?
 In order to make such a calculation, we must
first specify what constitutes a quantitative
removal. The decision here is arbitrary and
depends on the purpose of the separation.
 In this example. we shall consider a
separation to be quantitative when all but 1
part in 1000 of the Cd2+ has been removed;
that is, the concentration of the cation has
been lowered to 1.00 × 10-4 M.
Calculation:
 Substituting this value into the solubility-
product expression gives
 10-4 [S2-] = 1 × 10-27
 [S2-] = 2 × 10-23
 Thus, if we maintain the sulfide concentration
at this level or greater, the may assume that
quantitative removal of the cadmium will take
place.
Calculation(2)
 Next, we compute the [S2-] needed
to initiate precipitation of Tl2S from
a 0.1 M solution. Precipitation will
begin when the solubility product is
just exceeded. Since the solution is
0.1 in TI+,
 (0.1)2[S2-] = 6 × 10-22
 [S2-] = 6 × 10-20
 These two calculations show that quantitative
precipitation of Cd2+ takes place if [S2-] is made
greater than 1 x 10-23. No precipitation of TI+ occurs,
however, until [S2-] becomes greater than 6 x 10-20
M,
 Substituting these two values for [S2-] into Equation
7-23 permits calculation of the [H3O+] range required
for the separation.
Calculation:
 [H3O+]2 = 1.2 x 10-22/1 x 10-23 = 12
 [H3O+] = 3.5
 and
 [H3O+]2 = 1.2 X 10-22/6 x 10-20 = 2.0 x 10-3
 [H3O+] = 0.045
 By maintaining [H3O+] between
approximately 0.045 and 3.5 M, we can in
theory separate CdS quantitatively from TI2S.
Problems:
 Calculate the molar solubility of CuS in a
solution in which [H3O+] is held constant at
(a) 1.0 × 10-1 M; and (b) 1.0 × 10-4 M.

 The solubility-product constant for PbCO3 is

7.4 × 10-14. Calculate the equilibrium
solubility of PbCO3 in a solution that has a
constant hydronium ion concentration of
 (a) 1.00 × 10-3 M. (b) 1.00 × 10-10 M.
Problems:
 Silver ion is being considered as a reagent
for separating I- from SCN- in a solution that
is 0.060 M in KI and 0.070 M in NaSCN.
 (a) What Ag+ concentration is needed to
lower the I- concentration to 1.0 × 10-6 M?
 (b) What is the Ag+ concentration of the
solution when AgSCN begins to precipitate?
 (c) What is the ratio of SCN- to I- ion when
AgSCN begins to precipitate?
 (d) What is the ratio of SCN- to I- when the
Ag+ concentration is 1.0 × 10-3 M?