CHAPTER 16

Aqueous Ionic Equilibrium

skip 16.4

16.2 PROPERTIES OF BUFFERS

a solution that resists pH change
Buffers have large amounts of a weak acid and its
conjugate base
The weak acid reacts with added base.
The conjugate base reacts with added acid.
Buffer

16.2 ACETATE BUFFER

16.2 ACETATE BUFFER

NaOH + HC2H3O2 NaC2H3O2 + H2O
HCl + NaC2H3O2 HC2H3O2 + NaCl

16.2 BUFFER DEMO

#

Initial Solution

pH

Added

1.0 M HCl

0.0

0.5 M NaH2PO4
0.5 M Na2HPO4

6.9

10 mL 1.0 M HCl

pure H2O

7.0

0.5 M NaH2PO4
0.5 M Na2HPO4

6.9

10 mL 1.0 M NaOH

1.0 M NaOH

14.0

color
pH

16.2 COMMON ION

Consider

the NaF/HF buffer:

NaF (s) Na+ (aq) + F (aq)

HF (aq) H+ (aq) + F (aq)

The

common ion is F.

16.2 COMMON ION EFFECT

Ion Effect equilibrium shift from addition
of an ion in the equilibrium reaction
Le Chteliers principle
Common

HF (aq) H+ (aq) + F (aq)

[HF]0

[NaF]0

[H3O+]

%
dissociated

1.0 M

0M

2.7 102 M

2.7%

1.0 M

1.0 M

7.2 104 M

0.072%

16.2 HENDERSON-HASSELBALCH EQUATION

Calculating

buffer pH is simplified by this equation, which

is only used if the x is small approximation is valid.

[conjugate base anion] initial

pH pK a log
[weak acid] initial

16.2 HENDERSON-HASSELBALCH EQUATION

[A - ][ H3O ]
Ka
HA
[HA]

[H3O ] K a -
[A ]

[A [HA]
] [HA]
[HA]

p]Ka
log
KKa
log
log
log[ pH
H3OpH
pK
log

a
a
- ][A
- ]
[HA]
[A- ][A

pH - log[H 3O ] pK a -[HA]
log K a [A ]
-

log

[A ]

log

[HA]

16.2 SOLVING BUFFER PROBLEMS

Lets solve the same buffer problem using:

An ICE chart
The Henderson-Hasselbalch equation

16.2 ICE CHART

What is the pH of a solution that is 0.80 M HF (Ka = 7.2
104) and 1.6 M NaF?
HF(aq) + H2O(l) H3O+(aq) + F(aq)
initial

0.80

1.6

change

+x

+x

0.80 x
0.80

1.61.6
+x

equilibrium

x = 3.6 104
pH = log (3.6 104)
= 3.44
approximation valid

16.2 HENDERSON-HASSELBALCH EQUATION

What is the pH of a solution that is 0.80 M HF (Ka = 7.2
104) and 1.6 M NaF?

3.44 = 3.142 + 0.301

approximation valid

CALCULATE THE PH OF A BUFFER

0.20 M IN FORMIC ACID AND 0.15 M IN
SODIUM FORMATE (KA = 1.8 104).

pKa = log (1.8 104) = 3.74

[H3O+] = 103.62
= 2.4 104
approximation valid

16.2 CHANGES IN PH
Buffers

resist large pH changes when acid or base

are added but their pH does change.
To find the new pH after adding acid or base:
1. Do the stoichiometry: the moles of one buffer
ingredient is reduced, the moles of the other is
increased
2. Equilibrium calculation of [H3O+] using the new
initial values of [HA] and [A]

16.2 BUFFERS AT WORK

A

100.0 mL buffer solution is 0.175 M in HClO (Ka

= 2.81 108) and 0.150 M in NaClO.
What is the initial pH of this solution?

7.484 = 7.551 + (0.067)

What is the pH after adding 0.0010 mol HBr?

ClO + H+ HClO
I 0.150
F 0.140

0.010
0.000

0.175
0.185

7.430 = 7.551 + (0.121)

16.2 BUFFERS
Solutions

of a weak base and its conjugate acid

are also buffers.

16.2 BUFFERS AT WORK

1 L of a buffer is 0.320 M NH3 and 0.400 M NH4Cl (Ka =
5.75 1010); how many moles of HCl must be added to
drop the pH to 9.00?

I
F

NH3 + HCl NH4+Cl

0.320 0
0.400
0.320 x 0
0.400 + x

x = 0.057 mol HCl

16.3 BUFFER STRENGTH

Effective

buffers have:
weak acids with pKa close to the desired pH
equal concentrations of weak acid and
conjugate base.
higher concentrations of both acid and base
[HC
[HC22H
H33O
O22]]

[NaC
[NaC22H
H33O
O22]]

pH before
pH
0.01 mol H+

pH
pH after
after
0.01
0.01 mol
mol H
H++

11

1.00
5.00 M
M

1.00
5.00 M
M

4.74
4.74

4.73
4.74

22

0.010
0.050 M
M

0.050
1.00 MM

6.74
4.74

6.43
4.56

16.3 RANGE AND CAPACITY

range the pH range where a buffer is
most effective at resisting changes to pH, usually
1 the acids pKa
Buffer capacity the amount of acid or base that
can be added to a buffer before it loses its
effectiveness
Buffer

16.3 RANGE AND CAPACITY

H+ + A HA
not an equilibrium

HA + OH A + H2O
not an equilibrium

16.4 VOLUME CHANGING TITRATIONS

Calculating

the pH curve for a titration is one of

the most tedious tasks in this class.
Heres how to calculate a single point:

original
pH

stoichiometry
calculation

titrant
added

new
pH

equilibrium
calculation

16.4 VOLUME CHANGING TITRATIONS

50.0 mL of 0.10 M acetic acid (Ka = 1.8 105) is
titrated with 0.10 M NaOH. Find the pH after 10.0
mL of 0.10 M NaOH was added.

I
F

HC2H3O2 + NaOH
5.0
1.0
4.0
0

NaC2H3O2 + H2O
0
1.0

An IF chart tabulates Initial and Final mmol of reactants and

products. This is a stoichiometry not an equilibrium problem.

HC2H3O2 (4.0 mmol) NaC2H3O2 (1.0 mmol)

16.4 VOLUME CHANGING TITRATIONS

50.0 mL of 0.10 M acetic acid (Ka = 1.8 105) is
titrated with 0.10 M NaOH. Find the pH after 10.0
mL of 0.10 M NaOH was added.
HC2H3O2 + H2O C2H3O2 + H3O+
initial
change
equilibrium

4.0/60.0
0.0667

1.0/60.0
0.0167

+x

+x

0.0667
0.0667x

0.0167+x
0.0167

x = 7.19 105

approximation valid

pH = log (7.19 105)

= 4.14

16.5 SOLUBILITY
All

ionic compounds dissolve

in water to some degree.
Some have such low water
solubility we classify them as
insoluble.
Water solubilities can be
found using equilibrium
calculations.

16.5 SOLUBILITY RULES

16.5 SOLUBILITY PRODUCT CONSTANT (Ksp)

Product, Ksp the equilibrium
constant for the dissociation of a salt into its
aqueous ions.

Solubility

MnXm(s) n Mm+ (aq) + m Xn (aq)

Ksp = [Mm+]n[Xn]m
For

example:

PbCl2(s) Pb2+ (aq) + 2 Cl (aq)

Ksp = [Pb2+][Cl]2

16.5 MOLAR SOLUBILITY

Solubility

the amount of solute that will

dissolve in a given amount of solution
Molar Solubility solubility expressed in mol/L
or M

m
molar solubility

K sp
n

16.5 SOLUBILITY
is the molar solubility of MX (Ksp = 1.27
1036)?

What

MX(s) M+(aq) + X(aq)

initial

change

+x

+x

equilibrium

Ksp = 1.27 1036 = x x

x = 1.13 1018 = [M+] = [X] = molar solubility

16.5 SOLUBILITY
Molar

solubility is related to

Ksp
You cant compare
solubilities of compounds
by Ksp unless they produce
the same number of ions.

Ag2CO3 > Ag3PO4 > AgI

16.5 RELATIVE SOLUBILITY

Order these by increasing solubility:
Ag3PO4
Ksp = 1.8 1018
Ag2CO3
Ksp = 8.1 1012
AgI
Ksp = 1.5 1016
Ag3PO4 3 Ag+ + PO43
x +3x
+x

Ksp = [Ag+]3[PO43]
1.8 1018 =(3x)3x
x = 1.6 105

Ag2CO3 2 Ag+ + CO32

x +2x
+x

Ksp = [Ag+]2[CO32]
8.1 1012 =(2x)2x
x = 1.3 104

AgI Ag+ + I
x
+x +x

Ksp = [Ag+][I]
1.5 1016 = x x
x = 1.2 108

16.5 MOLAR SOLUBILITY

Solubility

the amount of solute that will

dissolve in a given amount of solution
Molar Solubility solubility expressed in mol/L
or M

m
molar solubility

K sp
n

16.5 MOLAR SOLUBILITY

If the solubility of CuCl is 3.91 mg per 100.0 mL of
solution, calculate its Ksp.
CuCl(s) Cu+ (aq) + Cl(aq)

16.5 COMMON IONS AND SOLUBILITY

Ionic

compounds (MX) decrease in solubility

when a common ion (M+ or X) is added.
Addition of Ag+ shifts the equilibrium to the left
(LeChtelier):

Ag2CrO4(s) Ag+ (aq) + 2 CrO4(aq)

[AgNO3]

Ag2CrO4 solubility

1.3 104 M

0.100 M

9.0 1010 M

16.5 COMMON IONS AND SOLUBILITY

Calculate

the solubility of solid Pb3(PO4)2 (Ksp =

1.0 10-54) in a 0.10 M Pb(NO3)2 solution.
Pb3(PO4)2(s) 3 Pb2+(aq) + 2 PO43(aq)
I
0.10 0
C +3x +2x
E 0.10 + 3x 2x

16.5 EFFECT OF PH ON SOLUBILITY

Insoluble

ionic compounds with basic anions and

more soluble in low pH.

ZnF2(s) Zn2+(aq) + 2 F(aq)

H3O+(aq) + F(aq) HF(aq) + H2O(l)

16.6 PRECIPITATION
Precipitation

occurs when concentrations of the

ions exceeds the solubility of the ionic compound.
Compare reaction quotient Q for the current
solution concentrations to the value of Ksp:
Q = Ksp, saturated, no ppt
Q < Ksp, unsaturated, no ppt
Q > Ksp, above saturation, ppt

16.6 SUPERSATURATION
This

solution is supersaturated in sodium acetate.

Solid formation is triggered by any impurity, such
as a dust particle.

16.6 PRECIPITATION
1.20 g of solid NaCl is added to 95 mL of a solution 0.0012
M in Pb2+. Does PbCl2 (Ksp = 1.6 10-5) precipitate, and if
yes, what are the equilibrium concentrations of Pb2+ and
Cl?
Q = [Pb2+][Cl]2
PbCl2(s) Pb2+ (aq) + 2 Cl(aq)
I
0.0012
0.216
F
0
0.216 2(0.0012) = 0.214 M

Q = (0.0012)(0.216)2 = 5.6 10-5 > Ksp

a ppt
forms

16.6 PRECIPITATION
1.20 g of solid NaCl is added to 95 mL of a solution 0.0012
M in Pb2+. Does PbCl2 (Ksp = 1.6 10-5) precipitate, and if
yes, what are the equilibrium concentrations of Pb2+ and
Cl?
PbCl2(s) Pb2+(aq) + 2 Cl(aq)
initial

0.214

change

+x

+2x

equilibrium

0.214
0.214
+ 2x

Ksp = [Pb2+][Cl]2 = 1.6 105 = x (0.214)2

x = [Pb2+] = 3.5 104 M

[Cl] = 0.214 2(3.5 104) = 0.213 M

16.6 PRECIPITATION REACTION SUMMARY

1.
2.

3.

4.

5.
6.

Find the initial concentrations of the ions.

Calculate Q to determine how the equilibrium will
shift.
If Q Ksp no precipitation occurs, if Q > Ksp,
continue to step 4.
Form as much solid as possible, at least one of
the ions will be completely reacted.
Calculate the excess ions concentration.
Determine the ion concentrations at equilibrium
using an ICE table.

16.4 PRECIPITATION REACTION

150.0 mL of 0.0100 M Mg(NO3)2 and 250.0 mL of
0.100 M NaF are mixed. Find [Mg2+] and [F] at
equilibrium (MgF2, Ksp = 6.4 109).

16.4 PRECIPITATION REACTION

150.0 mL of 0.0100 M Mg(NO3)2 and 250.0 mL of
0.100 M NaF are mixed. Find [Mg2+] and [F] at
equilibrium (MgF2, Ksp = 6.4 109).

I
F

MgF2(s) Mg2+(aq) + 2 F(aq)

1.50 25.0
0
22.0

16.4 PRECIPITATION REACTION

150.0 mL of 0.0100 M Mg(NO3)2 and 250.0 mL of
0.100 M NaF are mixed. Find [Mg2+] and [F] at
equilibrium (MgF2, Ksp = 6.4 109).

MgF2(s) Mg2+(aq) + 2 F(aq)

initial

0.0550

change

+x

+2x

equilibrium

0.0550
+ 2x
0.0550

EXAM II, 10/16/12

II covers Chapter 15.6 15.11, 16.
Skip indicators, equivalence point, pH curves
and volume-changing titrations (part of 16.4).
All equations and constants are provided.
Exam

16.6 SELECTIVE PRECIPITATION

Different

cations in solution can often be separated

by reagents that precipitate only one.

16.6 QUALITATIVE CHEMICAL ANALYSIS

16.8 COMPLEX IONS

Transition metal ions are often good Lewis acids.
Complex Ion transition metal ion-ligand complex
Ligand a small molecule/ion with a lone pair that acts
as a Lewis base
CN, NH3, H2O, OH, halides

metal ion + ligands complex ion

Au3+ + 4 Cl AuCl4

16.8 COMPLEX ION EQUILIBRIA

Stronger ligands displace weaker ones:

Ag(H2O)2+(aq) + 2 NH3(aq) Ag(NH3)2+(aq) + 2 H2O(l)

H2O can be omitted, since its complex ion is always

present in aqueous solution:
Ag+(aq) + 2 NH3(aq) Ag(NH3)2+(aq)

16.8 FORMATION CONSTANT, Kf

Formation Constant, Kf the equilibrium constant for

the formation of a complex ion

Ag+(aq) + 2 NH3(aq) Ag(NH3)2+(aq)

16.8 FORMATION CONSTANT, Kf

Kf values are very large, assume reactions that form

complex ions go to completion and minor amounts of
uncomplexed M+ and ligand remain.

16.8 INVISIBLE INK

The use of invisible inks dates back to 100 AD Rome.
Most are activated by heat. They can be acids or
bases that darken the paper or heat-activated dyes.
In 2008, Britain convicted a man to a decade in prison
for possession of diaries with Al-Qaeda contact info
written in invisible ink.

Co2+ + 4 Cl CoCl42

16.8 COMPLEX ION EQUILIBRIA

0.10 mol AgNO3 is dissolved in 1.00 L of 1.00 M NH3. If
0.010 mol NaCl is added will AgCl precipitate? Kf
[Ag(NH3)2+] = 1.7 107; Ksp [AgCl] = 1.8 1010
Ag+(aq) + 2NH3(aq) Ag(NH3)2+(aq)

I
F

0.10
0

1.00
0.80

0
0.10

Ag+(aq) + 2NH3(aq) Ag(NH3)2+(aq)

initial

0.80

0.10

change

+x

+2x

equilibrium

0.80
0.80
+ 2x

0.10 x
0.10

16.8 COMPLEX ION EQUILIBRIA

0.10 mol AgNO3 is dissolved in 1.00 L of 1.00 M NH3. If
0.010 mol NaCl is added will AgCl precipitate? Kf
[Ag(NH3)2+] = 1.7 107; Ksp [AgCl] = 1.8 1010
x = [Ag+] =
9.8 109 M

AgCl(s) Ag+(aq) + Cl(aq)

Qsp = [Ag+][Cl] = (9.8 109)(0.010) = 9.8 1011
Ag+(aq) + 2NH3(aq) Ag(NH3)2+(aq)

initial
change
equilibrium

0.80

0.10

9.8 +x
1011 < 1.8+2x
1010 x
Q < Ksp
0.80
0.10 x
x sp 0.80
+ 2x
0.10
no ppt

If the molar solubility of AgI in 3.0 M NH3 is 1.5 104

M, the molar solubility of AgI in pure water is

1.
2.
3.

higher
the same
lower

33%

33%

33%
solvent
pure water
3.0 M NH3

solubility
1.2 108 M
1.5 104 M

:30

16.8 COMPLEX ION EQUILIBRIA

Calculate the molar solubility of AgI in 3.0 M NH3. Kf
[Ag(NH3)2+] = 1.7 107, Ksp [AgI] = 1.5 1016
AgI(s) Ag+ (aq) + I (aq)
Ag+(aq) + 2NH3(aq) Ag(NH3)2+ (aq)
AgI(s) + 2NH3(aq) Ag(NH3)2+(aq) + I (aq)
AgI

Ksp = 1.5 1016

Kf = 1.7 107
Ksp Kf

2NH3 Ag(NH3)2+ +

initial

3.0

change

2x

+x

+x

3.03.0
2x

equilibrium

x = 1.5 104 M