Jessica Sproul

Chapter 10 Summary
Dr. Rahni
Analytical Chemistry

How Equilibrium Calculations Can Be Applied to Complex

Systems

10A) Solving Multiple-Equilibrium Problems by a Systematic

Method

1) Aqueous solutions encountered in the lab often contain several species

that interact with one another and water to yield two or more equilibria that

function simultaneously.

2) When water is saturated with barium sulfate, three equilibria evolve:

BsSO4(s)  Ba2+ + SO42-

SO42- + H3O+  HSO4- + H2O

2H2O  H3O+ + OH-

i) These equilibria will shift accordingly if ions are added.

3) Solution of a multiple-equilibrium problem requires as many independents

equations as there are participants in the system being studied. In the

above system, there are five species: Ba2+, SO42-, HSO4-, H3O+, and OH-.

In order to calculate the solubility of barium sulfate, there needs to be five

independent algebraic equations.

4) There are three types of algebraic equations:

i) Equilibrium-constant expressions

ii) Mass-balance expressions

 iii) Charge-balance expressions

10A-1) Mass-Balance Equation

1) Mass-balance equations relate the equilibrium concentrations of

various species in a solution to one another and to the analytical

concentrations of the various solutes.

Example 10-1

Write mass-balance expressions for a 0.0100 M solution of HCl that is in

equilibrium with an excess of solid BaSO4.

From our general knowledge of the behavior of aqueous solutions, we can

write equations for three equilibria that must be present in this solution.

BsSO4(s)  Ba2+ + SO42-

SO42- + H3O+  HSO4- + H2O

2H2O  H3O+ + OH-

Because the only source for the two sulfate species is the dissolved

BsSO4, the barium ion concentration must equal the total concentration of

sulfate-containing species, and a mass-balance equation can be written that

expresses this equality. Thus

[Ba2+] = [SO42-] + [HSO4]

The hydronium ion concentration in this solution has two sources: one

from the HCl and the other from the dissociation of the solvent. A second mass-

balance equation expression is this

[H3O+] + [HSO4-] = cHCl + [OH-] = 0.0100 + [OH-]

 Since the only source of hydroxide is the dissociation of water, [OH -] is

equal to the hydronium ion concentration from the dissociation of water.

Example 10-2

Write mass-balance expressions for the system formed when a 0.010 M

NH3 solution is saturated AgBr.

Here, equations for the pertinent equilibria in the solution are

AgBr(s)  Ag+ + Br -

Ag+ + 2NH3  Ag(NH3)2+

NH3 + H2O  NH4+ + OH-

2H2O  H3O+ + OH-

Because the only source of Ag+, Br -, and Ag(NH3)2+ is AgBr and because

silver and bromide ions are present in a 1:1 ration in that compound, it follows

that one mass-balance equation is

[Ag+] + [Ag(NH3)2+] = [Br -]

where the bracketed terms are molar species concentration. Also, we know that

the only source of ammonia-containing species is the 0.010 M NH 3. Therefore,

c NH3 = [NH3] + [NH4+] + 2[Ag(NH3)2+] = 0.010

From the last two equilibria, we see that the one hydroxide ion is formed

for each NH4+ and each hydronium ion. Therefore,

[OH-] = [NH4+] + [H3O+]

10A-2) Charge-Balance Equation

1) Solutions are neutral because the molar concentration of positive charge

in an electrolyte solution always equals the molar concentration of

negative charge.

# mol/L positive charge = # mol/L negative charge

2) The concentration of charge contributed to a solution by an ion is equal to

the molar concentration of that ion multiplied by its charge.

i) For Na+

mol positive charge/L = (1 mol positive charge/mol Na +) X (mol Na+/L)

= 1 X [Na+]

ii) For Mg2+

mol positive charge/L = (2 mol positive charge/mol Mg 2+) X (mol Mg2+/L)

= 2 X [Mg2+]

iii) For PO43-

mol positive charge/L = (3 mol positive charge/mol PO 43-) X (mol PO43-/L)

= 3 X [PO43-]

3) Now consider how we would write a charge-balance equation for a 0.100

M solution of sodium chloride. Positive charges are supplied by the Na +

and the H3O+ (from the dissociation of water). Negative charges are

supplied by the Cl- and the OH-. The molarities of positive and negative

charges are

mol positive charge/L = [Na+] + [H3O+] = 0.100 + 1 X 10-7

mol positive charge/L = [Cl-] + [OH-] = 0.100 + 1 X 10-7

 We write the charge-balance equation by equating the concentrations of

positive and negative charges. That is,

[Na+] + [H3O+] = [Cl-] + [OH-] = 0.100 + 1 X 10-7

4) The charge-balance equations for the aqueous solutions constrain the

unknown 's to be such that, when the 's are added to the original data,

charge balance is produced in each aqueous solution. The charge-

balance equation for an aqueous solution is

, (137)

where is the charge imbalance in aqueous solution q calculated by a

speciation calculation and is defined to be the charge on the master

species plus the alkalinity assigned to the master species,

. For alkalinity, is defined to be -1.0. The

summation ranges over all elements or element valence states and

includes a term for alkalinity, just as charge balance is commonly

calculated by summing over cationic and anionic elements plus a

contribution from alkalinity. In the definition of , the alkalinity of the

master species is added to the charge for that master species to remove

the equivalents for the element or element redox state that are already
 accounted for in the alkalinity. For example, the contribution of carbonate

species in equation 137 is zero with this definition of ( ,

, ); all of the charge contribution of carbonate

species is included in the alkalinity term of the summation.

(http://wwwbrr.cr.usgs.gov/projects/GWC_coupled/phreeqc/html/final-26.html)

Example 10-3

Write a charge-balance equation for the system in Example 10-2.

[Ag+] + [Ag(NH3)2+] + [H3O+] + [NH4+] = [OH-] + [Br -]

Example 10-4

Neglecting the dissociation of water, write a charge-balance equation for a

solution that contains NaCl, Ba(ClO4)2, and Al2(SO4)3.

[Na+] + 2[Ba2+] + 3[Al3+] = [Cl-] + [ClO4-] + 2[SO42-]

10A-3) Steps for Solving Problems Involving Several Equilibria

1) Write a set of balanced chemical equations for all pertinent equilibria.

2) Sate in terms of equilibrium concentrations what quantity is being sought.

3) Write equilibrium-constant expressions for all equilibria developed in step

1 and find numerical values for the constants in tables of equilibrium

constants.

4) Write mass-balance expressions for the system.

5) If possible, write a charge-balance expression for the system.

6) If the number of unknown concentrations is equal to the number of

equations at this point, proceed on to step 7. If the number of unknown

concentrations is greater than the number of equations, seek additional

equations. If there are no possible equations to be found and suitable

assumptions regarding the

unknowns cannot be made, the

problem cannot be solved.

7) Make suitable approximations to

simplify the algebra.

8) Sole the algebraic equations for the

equilibrium concentrations needed

to give a provisional answer as

defined in step 2.

9) Check the validity of the

approximations made in step 7

using the provisional concentrations

computed in step 8.
10A-4) Making Approximations to Solve Equilibrium Equations

1) When step 6 is completed, there is the mathematical problem of

solving several nonlinear simultaneous equations.

2) Without computer help, solving this complex system is formidable,

tedious, and time consuming.

3) Approximations can allow a complex system to be solved much

more easily.

4) Only the mass-balance and charge-balance equations can be

simplified because they involve only sums and differences, not products

and quotients.

5) With enough knowledge of the chemistry of a system, it is possible

to assume that a given term in a mass-balance or charge-balance

equation is sufficiently small that it can be neglected.

i) In a solution containing a reasonable concentration of an acid,

the hydroxide concentration will often be negligible with respect

to many other species in the solution and the term for the

hydroxide concentration can usually be neglected in a mass- or

charge-balance expression without introducing a significant

error in the calculations.

6) Never be afraid to make an assumption in attempting to solve an

equilibrium problem. If the assumption is not valid, you will know it as

soon as you have an approximate answer.

10B) Calculating Solubilities by the Systematic Method

10B-1) Solubility Calculations

Example 10-5

Calculate the molar solubility of Mg(OH2) in water.

Step 1. Pertinent Equilibria

Two equilibria that need to be considered are

Mg(OH2)(s)  Mg2+ + 2OH-

2H2O  H3O+ + OH-

Step 2. Definition of the Unknown

Since 1 mol of Mg2+ is formed for each mole of Mg(OH2) dissolved,

Solubility Mg(OH2) = [Mg2+]

Step 3. Equilibrium-Constant Expression

Ksp = [Mg2+][OH-]2 = 7.1 X 10-12

Ksp = [H3O+][OH-] = 1.00 X 10-14

Step 4. Mass-Balance Expression

As shown by the two equilibrium equations, there are two sources of hydroxide

ions: Mg(OH2) and H2O. The hydroxide ion resulting from the dissociation of

Mg(OH2) is twice the magnesium ion concentration and that from the dissociation

of water is equal to the hydronium ion concentration. Thus,

[OH-] = 2[Mg2+] + [H3O+]

Step 5. Charge-Balance Expression

[OH-] = 2[Mg2+] + [H3O+]

Not that this equation is identical to the mass-balance equation. Often a mass-

balance equation and a charge-balance equation are the same.

Step 6. Number of Independent Equations and Unknowns

We have developed three indepencent algebraic equations and have three

unknowns([OH-], [Mg2+] and [H3O+]). Therefore, the problem can be solved

rigorously.

Step 7. Approximations

We can make approximations only in the mass-balance equation. Since the

solubility-product constant for Mg(OH2) is relatively large, the solution will be

somewhat basic. Therefore, it is reasonable to assume that [H 3O+] is much less

than [OH-]. The mass-balance equation then simplifies to

2[Mg2+] = [OH-]

Step 8. Solution to Equations

Substitution of the approximation into the first equilibrium-constant expression

gives

[Mg2+](2[Mg2+])2 = 7.1 X 10-12

[Mg2+]3 = (7.1 X 10-12) / 4 = 1.78 X 10-12

[Mg2+] = solubility = 1.21 X 10-4 or 1.2 X 10-4 M

Step 9. Check of Assumptions

Substitution into the approximation equation yields

[OH-] = 2 X 1.21 X 10-4 = 2.42 X 10-4

[H3O+] = (1.00 X 10-14) / (2.42 X 10-4) = 4.1 X 10-11

Thus, our assumption that 4.1 X 10-11 is much less than 2.42 X 10-4 is certainly

valid.

10B-2) How pH Influences Stability

i) The solubility of a precipitate containing an anion with basic

properties, a cation with acidic properties, or both, will depend

on pH.

1) Solubility Calculations at Constant pH

Example 10-5

Calculate the molar solubility of calcium oxalate in a solution that has been

buffered so that is pH is constant and equal to 4.00.

Step 1. Pertinent Equilibria

CaC2O4(s)  Ca2+ + C2O42-

Oxalate ions react with water to form HC2O4- and H2C2O4. Thus, there three other

equilibria present in this solution.

H2C2O4 + H2O  H3O+ + HC2O4-

HC2O4- + H2O  H3O+ + C2O42-

2H2O  H3O+ + OH-

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 Expression

[Ca2+][C2O42-] = Ksp = 1.7 X 10-9

 ([H3O+][HC2O4-])/[H2C2O4] = K1 = 5.60 X 10-2

([H3O+][C2O42-])/[HC2O4-] = K2 = 5.42 X 10-5

[H3O+][OH-] = Kw = 1.0 X 10-14

Step 4. Mass-Balance Expression

Because CaC2O4 is the only source of Ca2+ and the three oxalate species,

[Ca2+] = [H2C2O4] + [HC2O4-] + [C2O42-]

Moreover, the problem states that the pH is 4.00. Thus,

[H3O+] = 1.00 X 10-4 and [OH-] = Ksp/[H3O+] = 1.00 X 10-10

Step 5. Charge-Balance Expression

A buffer is required to maintain th pH at 4.00. The buffer most likely consists of

some weak acid HA and its conjugate base, A-. The identities of the three

species and their concentrations have not been specified, however, so we do not

have enough information to write a charge-balance expression.

Step 6. Number of Independent Equations and Unknowns

We have four unknowns ([Ca2+], [H2C2O4], [HC2O4-], and [C2O42-]) as well as four

independent algebraic relationships. Therefore, an exact solution can be

obtained, and the problem becomes one of algebra.

Step 7. Approximations

An exact solution is so readily obtained in this case that we will not bother with

approximations.

Step 8. Solution to Equations

A convenient was to solve the problem is to substitute two of the equilibrium-

constant expressions into the mass-balance expression in such a way as to

develop a relationship between. Thus, we rearrange an equilibrium-constant

expression to give

[HC2O4-] = ([H3O+][C2O42-]) / K2

Substituting numerical values for [H3O+] and K2 gives

[HC2O4-] = (1.00 X 10-4[C2O42-]) / 5.42 X 10-5 = 1.85[C2O42-]

Substituting this relationship into another mass-balance expression and

rearranging gives

[H2C2O4] = ([H3O+][C2O42-]•1.85) / K1

Substituting numerical values for [H3O+] and K1 gives

[H2C2O4] = (1.85 X 10-4[C2O42-]) / 5.60 X 10-2 = 3.30 X 10-3 [C2O42-]

Substituting these expressions for [HC2O4-] and [H2C2O4] into the mass-balance

equation gives

[Ca2+] = 1.85[C2O42-] + 3.30 X 10-3 [C2O42-] + [C2O42-] = 2.85 [C2O42-]

or

[C2O42-] = [Ca2+] / 2.85

Substituting into the first equilibrium-constant expression gives

([Ca2+][Ca2+]) / 2.85 = 1.7 X 10-9

[Ca2+] = solubility = sqrt (2.85 X 1.7 X 10-9) = 7.0 X 10-5 M

2) Solubility Calculations When the pH is Variable

i) Solving the system when the pH is unknown is considerably

more difficult. Since the concentrations of [H 3O+] and [OH-] are

unknown, there would be two more unknowns. To solve this.

 Two additional expressions would be needed. To solve this

system would be tedious and time-consuming.

10B-3) The Solubility of Precipitates in the Presence of Complexing

Agents

i) 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.

1) Complex Formation with a Common Ion

i) Many precipitates react with the precipitating agent to form

soluble complexes.

ii) Increases in solubility caused by large excesses of a common

ion are not unusual.

2) Quantitative Treatment of the Effect of Complex

Formation on Solubility

i) Solubility calculations for a precipitate in the presence of a

complexing reagent are similar in principle to those discussed in

the previous section.

10C) Separating Ions by pH Control: Sulfide Separations

1) Several precipitating agents permit

separation of ions based on solubility differences. This requires close

control over the reacting agent at a suitable and predetermined lever. This

is often done by controlling the pH with suitable buffers.

Example 10-7
Calcium sulfide is less soluble than thallium sulfide (I). Find the condition under

which Cd2+ and Tl+ can, in theory, be separated quantitatively with H 2S from a

solution that is 0.1 M in each cation.

The constants for the two solubility equilibria are

CdS(s)  Cd2+ + S2- [Cd2+][S2-] = 1 X 10-27

Tl2S(s)  2Tl+ + S2- [2Tl+][S2-] = 6 X 10-22

Since CdS precipitates at a lower [S 2-] than does Tl2S, we first compute the

sulfide ion concentration necessary for quantitative removal of Cd 2+ from solution.

To make such a calculation, we must first speciful what constitutes a quantitative

removal. The decision 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 X 10 -4 M. Substituting this

into the solubility-product expression gives

10-4 [S2-] = 1 X 10-27

[S2-] = 2 X 10-23

Thus, if we maintain the sulfide concentration at this level or greater, we may

assume that quantitative removal of the cadmium will take place. 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 M in Tl+,

(0.1)2[S2-] = 6 X 10-22

[S2-] = 6 X 10-20
These two calculations show that quantitative precipitation of Cd 2+ takes place if

[S2-] is made greater than 1 X 10-23. No precipitation of Tl+ occurs, however, until

[S2-] becomes greater than 6 X 10-20 M.

Substituting these two values for [S 2-] into a previous equation permits the

calculation of the [H3O+] range required for separation.

[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 Tl2S.