Chapter 17 - Additional Aspects of Aqueous Equilibria

The Common Ion Effect

The solubility oI a partially soluble salt is decreased when a common ion is added.
Consider the equilibrium established when acetic acid, HC
2
H
3
O
2
, is added to water.
At equilibrium H

and C
2
H
3
O
2
-
are constantly moving into and out oI solution, but the
concentrations oI ions is constant and equal.
Consider the addition oI C
2
H
3
O
2
-
, which is a common ion. (The source oI acetate could be a
strong electrolyte such as NaC
2
H
3
O
2
.)
ThereIore, |C
2
H
3
O
2
-
| increases and the system is no longer at equilibrium.
HC
2
H
3
O
2
H

C
2
H
3
O
2
-
The equilibrium will
So, |H

| must

Buffered Solutions (Buffers)
Composition and Action of Buffered Solutions
A buIIer consists oI a mixture oI


The Ka expression is


A buIIer

When OH
-
is added to the buIIer,


When H

is added to the buIIer

Example
Write the reaction that occurs in a buIIer solution containing HF/F
-
when:
1. H

is added
2. OH
-
is added


Buffer Capacity and pH
BuIIer capacity is

BuIIer capacity depends on the composition oI the buIIer.
The greater the amounts oI conjugate acid-base pair, the greater the buIIer capacity.
The pH oI the buIIer depends on K
a
.




Addition of Strong Acids or Bases to Buffers
We break the calculation into two parts: stoichiometric and equilibrium.
The amount oI strong acid or base added results in a neutralization reaction:
X
-
H3O

HX H
2
O
go left
decrease
resists a change in ph when a small amount of OH- or H+ is added
the OH- reacts with the HX to produce X- and water but the [HX]/[X-] ratio remains more or less
constant, so the pH is not significantly changed.
X- is consumed to produce HX. Once again the [HX ratio remains constant pH does not change
significantly
weak acid and conj base
[H+][X-]/[HX]
H+---> HF
OH-+HF---->F-+h2o
the amount of acid or base neutralized by the buffer before there is a significant
change in pH
-log[H+]=-logKa-log([HX]/[x-])
ph=pKa+log[X]/[HX]
HX OH
-
X
-
H
2
O.
By knowing how much H
3
O

or OH
-
was added (stoichiometry) we know how much HX or
X
-
is Iormed. (SCF stoichiometry chart)
With the concentrations oI HX and X
-
(note the change in volume oI solution) we can
calculate the pH Irom the Henderson-Hasselbalch equation or the original equilibrium
expression (ICE chart).

Examples
1. Consider a buIIer prepared by placing 0.60 moles oI HF (K
a
7.2 x 10
-4
) and 0.48 moles oI
NaF in a 1.00 L solution.
a. Calculate the pH oI the buIIer
b. Calculte the pH aIter the addition oI 0.08 moles oI HCl
c. Calculate the pH aIter the addition oI a total oI 0.16 moles oI HCl
d. Calculate the pH aIter the addition oI 0.10 moles oI NaOH.














2. Consider a buIIer containing 0.78 moles oI HC
2
H
3
O
2
(K
a
1.8 x 10
-5
) and 0.67 moles oI
NaC
2
H
3
O
2
in 1.00 L oI solution.
a. Calculate the pH oI the buIIer solution.
b. Calculate the pH aIter the addition oI 0.10 moles oI HNO
3
.
c. Calculate the pH aIter the addtiion oI a total oI 0.20 moles oI HNO
3
.
d. Calculate the pH aIter the addition oI 0.10 moles oI NaOH.








Acid-Base Titrations

Strong Acid-Strong Base Titrations
A plot oI pH versus volume oI acid (or base) added is called a titration curve.
Consider adding a strong base (e.g. NaOH) to a solution oI a strong acid (e.g. HCl).
BeIore any base is added, the pH is given by the strong acid solution. ThereIore, pH
7.
When base is added, beIore the equivalence point, the pH is given by the amount oI
strong acid in excess. ThereIore, pH 7.
At equivalence point, the amount oI base added is stoichiometrically equivalent to the
amount oI acid originally present. ThereIore, the pH is determined by the salt
solution. ThereIore, pH 7.
Consider adding a strong base (e.g. NaOH) to a solution oI a strong acid (e.g. HCl).
We know the pH at equivalent point is 7.00.
To detect the equivalent point, we use an indicator that changes color somewhere near 7.00.

Calculations
Equivalence point: mol H

mol OH
-

pH beIore equivalence point:

pH at equivalence point 7
pH aIter equivalence point:

Examples
1. Consider the titration oI 50.0 mL oI 0.25 M HCl with 0.15 M
NaOH
a. Calculate the volume oI NaOH required to reach the equivalence point.
b. Calculate pH:
1. initially
2. aIter adding 25 mL NaOH
3. at the equivalence point
4. aIter adding 100 mL NaOH










2. Consider the titration oI 15.0 mL oI 0.50 M HNO3 with 0.25 M KOH.
a. Calculate the volume oI KOH required to reach the equivalence point.
b. Calculate the pH:
1. Initially
2. AIter the addition oI 10 mL KOH
3. AIter the addition oI 20 mL KOH
4. AIter the addition oI 30 mL KOH
5. AIter the addition oI 40 mL KOH
[H+]=molH+remaining/total volume
[OH-]=excess mol OH- added/total volume
HCl+NaOH--->H2O+NaCl
M1V1=M2V2
(0.25M)(50.0ml)=(0.15M)V2
V2=83ml
Strong Base - Strong Acid Titrations
The equivalence point in a titration is the point at which the acid and base
are present in stoichiometric quantities.
The end point in a titration is the observed point.
The diIIerence between equivalence point and end point is called the
titration error.
The shape oI a strong base-strong acid titration curve is very similar to a
strong acid-strong base titration curve.
Initially, the strong base is in excess, so the pH ~ 7.
As acid is added, the pH decreases but is still greater than 7.
At equivalence point, the pH is given by the salt solution (i.e. pH 7).
AIter equivalence point, the pH is given by the strong acid in excess, so pH 7.

Calculations
pH beIore equivalence point:

pH at equivalence point 7
pH aIter equivalence point:

Example Consider the titration oI 25.0 mL oI 0.30 M NaOH with 0.20 M HBr.
A. Calculate the volume oI HBr required to reach the equivalence point.
B. Calculate the pH:
1. Initially
2. AIter the addition oI 10 mL HBr
3. AIter the addition oI 20 mL HBr
4. At the equivalence point
5. AIter the addition oI 50 mL HBr










Weak Acid-Strong Base Titrations
Consider the titration oI acetic acid, HC
2
H
3
O
2
and NaOH.
BeIore any base is added, the solution contains only weak acid. ThereIore, pH is given by
the equilibrium calculation.
As strong base is added, the strong base consumes a stoichiometric quantity oI weak acid:


There is an excess oI acid beIore the equivalence point.
ThereIore, we have a mixture oI weak acid and its conjugate base.
The pH is given by the buIIer calculation.




At the equivalence point, all the acetic acid has been consumed and all the NaOH has been
consumed. However,
ThereIore, the pH is given by
This means pH ~ 7.
More importantly,

AIter the equivalence point, the pH is given by the strong base (OH
-
) in excess.

Calculations
At equivalence point, moles acid moles base
Initial pH pH oI a weak acid solution (ICE chart)
pH beIore equivalence point BuIIer Calculation


pH at equivalence point pH oI a weak base solution (ICE chart)
pH aIter equivalence point

Example
Consider the titration oI 50.0 mL oI 0.25 M HF with 0.15 M NaOH
a. Calculate the volume oI NaOH required to reach the equivalence point.
b. Calculate pH:
1. initially
2. aIter adding 25 mL NaOH
3. at the equivalence point
4. aIter adding 100 mL NaOH











For a strong acid-strong base titration, the pH begins at less than 7 and gradually increases as
base is added.
Near the equivalence point, the pH increases dramatically.
For a weak acid-strong base titration, the initial pH rise is more steep than the strong acid-
strong base case.
However, then there is a leveling oII due to buIIer eIIects.
The inIlection point is not as steep Ior a weak acid-strong base titration.
The shape oI the two curves aIter equivalence point is the same because pH is determined by
the strong base in excess.
Two Ieatures oI titration curves are aIIected by the strength oI the acid:
Weak acid strong base
the amount oI the initial rise in pH, and
the length oI the inIlection point at equivalence.
Type of Titration pH at Equivalence Point
Strong Acid and Strong Base
Strong Acid and Weak Base
Strong Base and Weak Acid
Weak Base and Weak Acid
II Ka~Kb,
II KaKb,

Titrations of Polyprotic Acids
In polyprotic acids, each ionizable proton dissociates in
steps.
ThereIore, in a titration there are n equivalence points
corresponding to each ionizable proton.
In the titration oI H
3
PO
3
with NaOH.
The Iirst proton dissociates to Iorm H
2
PO
3
-
.
Then the second proton dissociates to Iorm HPO
3
2-
.

Solubility Equilibria
The Solubility-Product Constant, K
sp

Consider

Ior which


K
sp
is the solubility product

In general: the solubility product is the molar concentration oI ions raised to their
stoichiometric powers.
Solubility is the amount (grams) oI substance that dissolves to Iorm a saturated solution.
Molar solubility is the number oI moles oI solute dissolving to Iorm a liter oI saturated
solution.

Solubility and K
sp

To convert solubility to K
sp

solubility needs to be converted into molar solubility (via molar mass);
molar solubility is converted into the molar concentration oI ions at equilibrium (equilibrium
calculation),
K
sp
is the product oI equilibrium concentration oI ions.



half equivalence pt is when the CB and A equal
pH=-logKa
Ksp=[Ba2+][SO42-]
Examples
1. The solubility oI calcium carbonate in water at 25C is 6.7 x 10
-3
g/L. Calculate the molar
solubility and K
sp
.

2. The solubility oI manganese (II) hydroxide in water at 25C is 3.42 x 10
-5
mol/L. Calculate
the solubility in g/L and calculate K
sp
.

3. K
sp
Ior PbF
2
at 25C is 3.6 x 10
-8
. Calculate the molar solubility and the solubility in g/L.

4. K
sp
Ior Ca
3
(PO
4
)
2
is 2.0 x 10
-29
. Calculate the molar solubility and the solubility in g/L.









Factors that Affect Solubility
The Common Ion Effect
Solubility is decreased when a common ion is added.
This is an application oI Le Chtelier`s principle:

as F
-
(Irom NaF, say) is added,

ThereIore,

As NaF is added to the system,

Examples
1. Calculate the solubility oI PbCl
2
(K
sp
1.7 x 10
-5
)
a. In water
b. In 0.50 M NaCl solution

2. Calculate the solubility oI Ag
2
SO
4
(K
sp
1.5 x 10
-5
)
a. In water
b. In 0.25 M AgNO
3
solution
c. In 0.20 M K
2
SO
4
solution





Solubility and pH
Again we apply Le Chtelier`s principle:

II the F
-
is removed
the solubility decreases
equilibrium shifts from the increase
CaF2 is formed
F
-
can be removed by adding a strong acid:

As pH decreases, |H

| increases and solubility increases.

The eIIect oI pH on solubility is dramatic.
Acidic salts are

Basic salts are

Formation of Complex Ions
A Consider the Iormation oI Ag(NH
3
)
2
:

The Ag(NH
3
)
2
is called a

NH
3
(the attached Lewis base) is called a

The equilibrium constant Ior the reaction is called the Iormation constant, K
f
:



Formation of Complex Ions
Consider the addition oI ammonia to AgCl (white precipitate):



The overall reaction is


EIIectively, the Ag

(aq) has been removed Irom solution.

By Le Chtelier`s principle,


Amphoterism
Amphoteric oxides will dissolve in either a strong acid or a strong base.
Examples: hydroxides and oxides oI Al
3
, Cr
3
, Zn
2
, and Sn
2
.
The hydroxides generally Iorm complex ions with Iour hydroxide ligands attached to the
metal:


Hydrated metal ions act as weak acids. Thus, the amphoterism is interrupted:


Precipitation and Separation of Ions


At any instant in time, Q |Ba
2
||SO
4
2-
|.
II Q K
sp
,

II Q K
sp
,

II Q ~ K
sp
,

Based on solubilities, ions can be selectively removed Irom solutions.
Consider a mixture oI Zn
2
(aq) and Cu
2
(aq). CuS (K
s
p 6 10
-37
) is less soluble than ZnS
(K
sp
2 10
-25
), CuS will be removed Irom solution beIore ZnS.
As H
2
S is added to the green solution, black CuS Iorms in a colorless solution oI Zn
2
(aq).
When more H
2
S is added, a second precipitate oI white ZnS Iorms.

Selective Precipitation of Ions
Ions can be separated Irom each other based on their salt solubilities.
Example: iI HCl is added to a solution containing Ag

and Cu
2
, the silver precipitates (K
sp

Ior AgCl is 1.8 10
-10
) while the Cu
2
remains in solution.
Removal oI one metal ion Irom a solution is called selective precipitation.

Qualitative analysis is designed to detect the presence oI metal
ions.
Quantitative analysis is designed to determine how much metal
ion is present.

Qualitative Analysis of metal ions
We can separate a complicated mixture oI ions into Iive
groups:
Add 6 M HCl to precipitate insoluble chlorides (AgCl,
Hg
2
Cl
2
, and PbCl
2
).
To the remaining mix oI cations, add H
2
S in 0.2 M HCl
to remove acid insoluble sulIides (e.g. CuS, Bi
2
S
3
,
CdS, PbS, HgS, etc.).
To the remaining mix, add (NH
4
)
2
S at pH 8 to remove base insoluble sulIides and
hydroxides (e.g. Al(OH)
3
, Fe(OH)
3
, ZnS, NiS, CoS, etc.).
To the remaining mixture add (NH
4
)
2
HPO
4
to remove insoluble phosphates
(Ba
3
(PO4)
2
, Ca
3
(PO
4
)
2
, MgNH
4
PO
4
).
The Iinal mixture contains alkali metal ions and NH
4

.

precipitation occurs
equilibrium
disassociation occurs