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Chapter 8B:

Systematic Treatment of Equilibrium


I. Introduction
Concentrations of individual species

Determining which species are present

Reactions

Equations

Steps in Figure 9-1


Example 9-1

BaSO4 (s) <=> Ba2+ + SO42-

2H2O <=> H3O+ + OH-

SO42 - + H3O+ <=> HSO4 - + H2O

HCl + H2O <=> H3O+ + Cl -


I. Introduction
Concentrations of individual species

Determining which species are present

Reactions

Equations

Assumption

Steps in Figure 9-1


A Systematic Method
II. A Systematic Method
for Solving Multiple Equilibria Problems

Equilibrium-constant expressions

Mass (concentration)-balance equations

A single charge-balance equation


Mass (concentration)-balance equations
Equilibrium concentrations of various species
in a solution to one another and to the analytical
concentration

Two Steps:

Reactions

Equations
Example 9-1:
Write mass-balance expressions for a 0.0100 M solution of HCl that is in
equilibrium with an excess of solid BaSO4(s).
BaSO4 (s) <=> Ba2+ + SO42-
HCl + H2O <=> H3O+ + Cl -
2H2O <=> H3O+ + OH-
SO42 - + H3O+ <=> HSO4- + H2O

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

[H3O+ ] = [Cl -]+[OH-]-[HSO4-] = CHCl + [OH-] - [HSO4-]


=0.0100 +[OH-] - [HSO4-]
[Cl -] = CHCl
Example 9-2:
Write mass-balance expressions for the system formed
when a 0.010 M NH3 solution is saturated with AgBr.
AgBr (s) <=> Ag+ + Br - [1]

Ag+ + 2NH3 <=> [Ag(NH3)2]+ [2]

NH3 + H 2O <=> NH4+ + OH - [3]

2H2O <=> H3O+ + OH- [4]

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


C NH3 = [NH3 ] + [NH4+ ] + 2[[Ag(NH3)2]+ ] = 0.010 M
[OH- ] = [NH4+ ] + [H3O+ ]
A single charge-balance equation
Solutions are neutral
The Sum of molar concentration of positive charge =
The sum of molar concentration of negative charge
Concentration of charge by an ion =
molar concentration of that ion x its charge

Steps:
List all ions in the solution and their charges and
concentrations
The Sum of molar concentration of positive charge =
The sum of molar concentration of negative charge
Example 9-1:
Write a charge-balance equation for a 0.0100 M solution of HCl
that is in equilibrium with an excess of solid BaSO4(s).
BaSO4 (s) <=> Ba2+ + SO42-
HCl + H2O <=> H3O+ + Cl -
2H2O <=> H3O+ + OH-
SO42 - + H3O+ <=> HSO4- + H2O

2[Ba2+] +[H3O+ ] = 2[SO42 - ]+[HSO4- ]+[OH-] + [Cl -]


Example 9-2:
Write a charge-balance equation for the system formed
when a 0.010 M NH3 solution is saturated with AgBr.
AgBr (s) <=> Ag+ + Br - [1]

Ag+ + 2NH3 <=> [Ag(NH3)2]+ [2]

NH3 + H2O <=> NH4+ + OH - [3]

2H2O <=> H3O+ + OH- [4]

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


Example 9-3:
Write a charge-balance equation for a 0.100 M solution of
NaCl
NaCl <=> Na+ + Cl-

2H2O <=> H3O+ + OH-

[Na+] +[H3O+ ] = [Cl -] + [OH-]

0.100 + 10-7 = 0.100 + 10-7


Example 9-4:
Write a charge-balance equation for a 0.100 M solution of
MgCl2

MgCl2 <==> Mg2+ + 2Cl-


2H2O <=> H3O+ + OH-

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

2 x 0.100 + 10-7 = 0.200 + 10-7


A Systematic Method
Steps for solving problems involving multiple equilibria

Pertinent Equilibria
The definition of unknown
Equilibrium Constant Expressions
Mass balance equation
Charge balance equation
Check No. of unknown species concentrations
and No of independent equations
Approximations:
Check of assumptions
Calculate unknown concentrations
III. Calculation of Solubility by the Systematic
Method

Metal Hydroxides (Examples 9-5)


The effect of pH on solubility
(1) pH is fixed (Example 9-6)
(2) pH is variable or unknown
(Examples 9-7)
Formation of Complex Ion
(Examples 9-8)
Separation of ions
(Examples 9-9)
Metal Hydroxides: Example 9-5:
Calculate the molar solubility of Fe(OH)3 in water.
1. Pertinent Equilibria:
Fe(OH)3 (s) < = = = > Fe+ 3 + 3 OH-
2 H2 O (l) < = = = = > H3 O+ + OH-
2. The definition of unknown:
Molar solubility Fe(OH)3 = [Fe+ 3 ]
3. Equilibrium Constant Expressions
Ksp = [Fe+ 3 ][OH-]3 = 2 x 10 -39 [Eq 1]
Kw = [H3 O+ ][OH-] = 1 x 10 -14 [Eq 2]
4. Mass balance equation
[H3O+ ] + 3[Fe+ 3] = [OH-] [Eq 3]
5. Charge balance equation
[H3O+ ] + 3[Fe+ 3] = [OH-] [Eq 4]
6. 3 chemical species ([Fe+ 3], [OH-], [H3O+ ])
3 independent equations
7. Approximations:
First assume [H3O+] << 3[Fe+3]
Then Eq 3: [H3O+] + 3[Fe+3] = [OH-] becomes
3[Fe+3] = [OH-]
substituting [OH-] = 3[Fe+3] into Eq. 1:
[Fe+3][OH-]3 = Ksp = 2 x 10-39
27 {[Fe+3]}4 = 2 x 10-39
[Fe+3] = 9 x 10-11 M molar solubility
8. Check of assumptions:
Our assumption for Eq 3 was
[OH-] = 3[Fe+3]
[OH-] = 3(9 x 10-11) = 3 x 10-10
14
K 1x10 5
[ H 3O + ] = w
- = 11 = 3x10 M
[OH ] 3x10
3 x 10-5 is not less than 3 x 10-10 so that
actually 3[Fe+3] << [H3O+] and Eq 3 becomes
[H3O+] = [OH-] = 1 x 10-7
9. Substituting this value for the [OH-] is Eq 1
39
K sp 2 x10 18
[ Fe 3+ ] = - 3 = 7 3 = 2 x10 M
[OH ] (1x10 )
In conclusion :
The effect of the self-ionization of water is
significant for relatively insoluble metal hydroxides
This is an example of the common ion effect !!!
Any Questions?
The effect of pH on solubility: (a) pH is fixed (known)
Example 9-6: Calculate the molar solubility of PbCO3 in a solution
buffered to a pH of 7.00.
1. Pertinent equilibria:
PbCO3 <=> Pb+2 + CO3-2 Ksp
H2CO3 + H2O <=> HCO3- + H3O+ Ka1
HCO3-+ H2O <=> CO3-2 + H3O+ Ka2
2. Definition of unknown: Solubility = [Pb+2]
3. Equilibrium Expressions
Ksp =[Pb+2][CO3-2] = 7.4 X 10-14
[H 3O + ][ HCO -3 ] [H 3O + ][CO 2-
3 ] 11
K a1 = = 4.45x107 K a2 = = 4.69 x10
[ H 2 CO 3 ] [ HCO -3 ]
4. Mass Balance Equation
[Pb+2] = [CO3-2] + [HCO3-] + [H2CO3]
5. Charge balance equation cannot be determined
because the buffer species have not been given,
6. Unknowns are [Pb+2], [CO3-2], [HCO3-], [H2CO3].
Four independent equations and four unknowns.
7. Approximations: not necessary because we can obtain an exact
equation based upon [H3 O+ ] = 1.0 X 10 -7
8. Solution:
[H 3O + ][CO 2-
3 ]
K a2 = - = 4.69 x1011
[ HCO 3 ]
[HCO3 -] = [H3 O+ ][CO3 -]/(4.69 X 10 -11 )
= (1.0 X 10 -7 M)[CO3 -2 ]/(4.69 X 10 -11 )
= 2.13 X 10 3 [CO3 -2 ]
[H 3O + ][ HCO -3 ]
K a1 = = 4.45x107
[ H 2 CO 3 ]
[H2 CO3 ] = [HCO3 -][H3 O+ ]/Ka1 =
(2.13 X 10 3 )[CO3 -2 ](1.0 X 10 -7 )/(4.45 X 10 -7 )
[H2 CO3 ] = 4.73 X 10 2 [CO3 -2 ]
substitute [HCO3 -] and [H2 CO3 ] into the mass balance equation:

[Pb+ 2 ] = [CO3 -2 ] + 2.13 X 10 3 [CO3 -2 ] + 4.73 X 10 2 [CO3 -2 ]

[CO3 -2 ] = [Pb+ 2 ]/(2.60 X 10 3 ) and substituting this into the


solubility product equation:
Solve solubility product equation:

Ksp = [Pb+2][CO3-2] = 7.4 X 10-14

[Pb 2+ ][Pb 2+ ] 14
3 = 7.4 x10
2.60 x10
[Pb+2]2 = 1.924 X 10-10

The solubility = [Pb+2] = 1.4 X 10-5 M


Any Questions?
The effect of pH on solubility: (b) pH is unknown
Example 9-7: Calculate the solubility of CuS in w ater.
1. Pertinent equilibria:
CuS <=> Cu+2 + S-2
S-2 + H2O <=> HS- + OH-
HS- + H2O <=> H2S + OH-
H2O <=> H3O+ + OH-
2. Definition of unknown: Solubility = [Cu+2]
3. Mass Balance Equation:
[Cu+2] = [S-2] + [HS-] + [H2S]
4. Charge Balance Equation:
2[Cu+2] + [H3O+] = 2[S-2] + [HS-] + [OH-]
5. Equilibrium Expressions:
Kw = [H3O+][OH-] = 1.00 X 10-14
[OH - ][ HS- ] K w 10 . x1014
K b1 = = = = 0.769
[S2- ] . x1014
K a2 13
[OH - ][ H 2S] K w 10 . x1014 7
K b2 = = = = 104
. x10
[ HS- ] K a1 9.6 x108
Ksp= [Cu+2][S-2] = 8 X 10-37
6 six unknowns and six equations:
7. Assumption:
First, we can see that the salt is fairly insoluble (Ksp = 8 X 10-37)
so we'll use assume [H3O+] = 10-7,
so that [Cu+2] << [H+] = 10-7

8. The charge balance equation


2[Cu+2] + [H3O+] = 2[S-2] + [HS-] + [OH-]
becomes:
[H3O+] = 2[S-2] + [HS-] + [OH-]

Also, due to low solubility, assume 2[S-2] + [HS-] << [OH-]


since we assume [H+] = 10-7 , [OH-] = 10-7
9. Equilibrium Expressions becomes:
[OH - ][ HS- ] [ HS- ] 0.769 0.769
K b1 = = 0.769 = - = 7 = 7.69 x10
6
[S2- ] [S2- ] [OH ] 10
[HS-] = 7.69 X 106 [S-2]

[OH - ][ H 2S] 7
K b2 = = 104
. x10
[ HS- ]
. x107 [ HS- ]
K b2 [ HS- ] 104
[ H 2S] = - = 7 = .
104[ HS -
] = 8.00 x10 6
[S 2-
]
[OH ] 10
10. Solve Equations:

[Cu+2] = [S-2] + [HS-] + [H2S]

[Cu+2] = [S-2] + (7.69 X 106)[S-2] + (8.00 X 106)[S-2]

[S-2] = 6.37 X 10-8 [Cu+2] substitute to Ksp equation

Ksp= [Cu+2][S-2]= 8 X 10-37

[Cu+2]2 = 1.3 x 10-29

[Cu+2] = 3.6 X 10-15 M

Note that solubility is increased due to the reaction of S-2


with H2O
Any Questions?
Review of Textbook for Chem115/116: Chapters
17 & 23: Complex (coordinate compound)
Coordinate covalent bonds: a bond formed when
both electrons of the bond are donated by one atom.
Ag+ + 2(:NH3) [H3N: Ag :NH3]+
Electron configuration of Ag [Kr]4d105s15P0
Ag+ [Kr]4d105s0 5P0
Sp hybrid orbitals: accommodate 2 pairs of electrons. Linear
Complex ion: A metal ion with Lewis base attached to
it through coordinate covalent bond.
Complex (Coordinate compound): a compound
consisting either of complex ions and other ions of
opposite charge or of neutral complex species.
Formation of Complex Ion: Example 9-8
The solubility product of CuI is 1.0x10-12. The formation constant K2
for the reaction of CuI with I- to give CuI2 is 7.9x10-4. Calculate the
molar solubility of CuI in a 1.0x10-4 M solution of KI.
Step 1. Pertinet Equilibria Step 4. Mass-balance Expression
CuI (s) <==> Cu+ + I-
[I-] = CKI + [Cu+] - [CuI2-]
CuI (s) + I- <==> CuI2-
KI K+ + I- Step 5. Charge-balance Equation
Step 2. Define of Unknown
[Cu+] + [K+] = [I-] + [CuI2-]
Solubility of CuI (s) = [Cu+] + [CuI2-]
[Cu+] + 1.0x10-4 = [I-] + [CuI2-]
Step 3. Equilibrium-Constant Expression
Ksp = [Cu+][I-] = 1.0x10-12
[CuI -2 ] 4
K2 = = 7.9 x10
[I - ]
Step 6. Number of Independent Equations and unknown
Three unknown: [Cu+], [I-], and [CuI2-]
Three independent equations
Step 7. Assumptions
[Cu+] << [I-] because Ksp of CuI is very small
[Cu+] - [CuI2-] << 1.0x10-4
Hence: Charge-Balance Equation is simplified as
[Cu+] + [K+] = [I-] + [CuI2-] [Cu+] + 1.0x10-4 = [I-] + [CuI2-]
[I-] = 1.0x10-4 + [Cu+] - [CuI2-] 1.0x10-4 M
Step 8. Solve Equations
Ksp = [Cu+][I-] = 1.0x10-12
[Cu+] = 1.0x10-12 / [I-] = 1.0x10-12 /1.0x10-4 = 1.0x10-8 M
[CuI -2 ] 4
K2 = = 7.9 x10
[I - ]
[CuI2-] = K2 [I-] = 7.9x10-4 x 1.0x10-4 = 7.9x10-8 M
[Cu+] = 1.0x10-8 M
[CuI2-] = 7.9x10-8 M

Solubility of CuI (s) = [Cu+] + [CuI2-] = 1.0x10-8 + 7.9x10-8


= 8.9x10-8 M

Step 9. Check Assumptions


[Cu+] << [I-] = 1.0x10-4 (True)
[Cu+] - [CuI2-] << 1.0x10-4 (True)

Both assumptions are correct. Therefore, our solubility calculated


based upon these two assumptions is valid!

Mission accomplished !!!


Any Questions?
VI. The Separation of Ions by Control of the Concentrat
of the Precipitating Reagent
A. Separation of metal hydroxides by controlling [OH-]

Example 9-9: Can Cu+2 be quantitatively separated from a


solution that is 0.100 M in Mg+2 by controlling pH?
for Cu(OH)2 Ksp= 4.8 x 10-20
for Mg(OH)2 Ksp= 7.1 x 10-12

1) Consider Cu(OH)2: At what [OH-] is [Cu+2] = 1 x 10-4 M?


[Cu+2][OH-]2 = 4.8 x 10-20

4.8 x1020 4.8 x1020


[OH - ] = 2+ = -4 = 4.8 x1016 = 2.2 x108 M
[Cu ] 1x10
14
K 10
. x10 7
[ H 3O + ] = w
- = 8 = 4.5 x10 M
[OH ] 2.2 x10
pH =-log [H3O+] = 6.3 which is fairly acid
2) Consider Mg(OH)2 :
At what pH=? is Mg+2 begins to precipitate

Ksp = [Mg+2][OH-]2 =[0.100 M][OH-]2 = 7.1 x 10-12

7.1x1012 7.1x1012
[OH - ] = 2+ = = 7.1x1011 = 8.4 x106 M
[ Mg ] 0.100

[OH-] = 8.4 x 10-6 M, which is fairly basic.


14
K .
10 x10 9
[ H 3O + ] = w
- = 6 = .
12 x10 M
[OH ] 8.4 x10

pH = -log [H3O+] = 8.9 which is fairly basic

Answer: Yes, we can quantitatively separate Cu+2 from


Mg+2 by keeping solution 6.3 <pH < 8.9
Any Questions?
Summary
9 Concepts of equilibrium
9 Equilibrium concentration of every species (e.g.,
ions, solubility) in the solution
9 Equilibrium-constant expressions
9 Mass (concentration)-balance equations
9 A single charge-balance equation
9 Calculation of Solubility by the Systematic Method
Metal Hydroxides
Formation of Complex Ion
Separation of ions
Homework
8-A, B, C, E, F, G, 2, 4, 11, 12, 18, 20, 24,
26

Before working on Homework,


Practice with all examples that we discussed in the class
and examples in the textbook!!