Chapter 17

Chapter 17: Solubility
Equilibria
Ketan Trivedi
www.trivedichemistry.com
Section 17.1-17.2: Solubility Equiliibria
and the K
sp
Table
In this chapter, we consider the equilibrium
associated with the dissociation of solids to
form aqueous solutions.
Our discussion is limited to ionic solids,
which release cations and anions upon
dissociation in water.
For example: Consider the equilibrium
dissolution of BaSO
4
.
BaSO
4 (s)
Ba
+2
(aq)
+ SO
4
-2
(aq)
and the K
sp
Table (cont.)
Initially, before solid BaSO
4
is added to water, the
Ba
+2
and SO
4
-2
ions are tightly bound to each other
in the crystalline lattice of the solid.
When the salt is placed in water, some of its Ba
+2
and SO
4
-2
ions are released into the solution.
This is expressed as: BaSO
4 (s)
Ba
+2
(aq)
+ SO
4
-2
(aq)
Now, if water is allowed to evaporate from the
solution, the molarities of Ba
+2
and SO
4
-2
ions in
solution may increase to the point where these ions
prefer to exist in combination as BaSO
4
solid.
This is expressed as: Ba
+2
(aq)
+ SO
4
-2
(aq)
BaSO
4 (s)
and the K
sp
Table (cont.)
In summary, as BaSO
4
is dissolved in water and
the concentrations of Ba
+2
and SO
4
-2
in solution
increase, a point may be reached where the solid
and the solution are in equilibrium.
This is expressed as: BaSO
4 (s)
Ba
+2
(aq)
+ SO
4
-2
(aq)
The point at which it becomes impossible to
dissolve any further amount of solid BaSO
4
in the
solution is called the saturation point. We say that
the solution is saturated.
and the K
sp
Table (cont.)
The equilibrium constant for this dissolution
process is expressed as:
K
sp
= [Ba
+2
][SO
4
-2
]
Note: Solids are not included in the equilibrium
constant expression.
K
sp
is called the solubility product constantor
simply the solubility product.
Note: Once the equilibrium is established, adding
more solid BaSO
4
to the solution will not shift the
position of the equilibrium.
and the K
sp
Table (cont.)
The Solubility of an ionic solid measures the
maximum amount of this solid that can be
dissolved in water at a given temperature.
The Solubility of an ionic solid is an equilibrium
property.
Thus, in pure water at a given temperature, an
ionic solid has a particular Solubility.
Solubility is expressed by the symbol S.
Solubility is expressed in the units of mol.L
-1
or
Molarity (M).
Section 17.5-17.6: The Common Ion
Effect in Solubility Problems
Let us consider a saturated solution of
BaSO
4
. The dissolution equilibrium for
BaSO
4
is represented as:
BaSO
4 (s)
Ba
+2
(aq)
+ SO
4
-2
(aq)
In a saturated solution of BaSO
4
, the
concentration of Ba
+2
and SO
4
-2
ions are
equal to the molar solubility of BaSO
4
.
Effect in Solubility Problems (cont.)
Now, what happens to this equilibrium if we add
Na
2
SO
4
or BaCl
2
?
Both Na
2
SO
4
and BaCl
2
are highly soluble in H
2
O.
For example, lets add Na
2
SO
4
to the saturated
solution of BaSO
4
.
The dissociation equation for Na
2
SO
4
is written as:
Na
2
SO
4 (s)
2 Na
+
(aq)
+ SO
4
-2
(aq)
Thus, adding Na
2
SO
4
to a saturated solution of
BaSO
4
results in an increase in the concentration
of SO
4
-2
.
Recall Le Chateliers Principle:
If a change is imposed on a system at
equilibrium, the system will react by shifting in the
direction that counteracts the change.
Thus, by increasing the concentration of
SO
4
-2
ions in solution, the dissolution
equilibrium shifts to the left (favoring the
formation of BaSO
4
).
Similarly, adding BaCl
2
to a saturated solution of
BaSO
4
results in an increase in the concentration
of Ba
+2
.
Hence, adding BaCl
2
will result in a shift of the
dissolution equilibrium for BaSO
4
in the direction
that consumes Ba
+2
.
In conclusion: the net effect of adding a common
ion to the saturated solution of a slightly soluble
ionic compound is to decrease its solubility (S) at a
given temperature.
Section 17.7: The Effect of pH on
Solubility
Consider a saturated solution of CaCO
3
. The
equation representing the dissolution equilibrium
for CaCO
3
is:
CaCO
3 (s)
Ca
+2
(aq)
+ CO
3
-2
(aq)
Now, CO
3
-2
is the conjugate base of carbonic acid,
H
2
CO
3
.
How do we know that?
This only comes through practice!!!
You should be familiar with strong, as well as
weak, acids and bases.
Solubility (cont.)
Carbonic acid, H
2
CO
3
, is a weak acid. Hence,
CO
3
-2
is a weak base.
Thus, if a strong acid is added to the CaCO
3
solution, then CO
3
-2
would accept a proton from the
acid.
Note: The addition of a strong acid reduces the pH.
The reaction between CO
3
-2
and H
+
is written as:
H
+
(aq)
+ CO
3
-2
(aq)
HCO
3
-
(aq)
Solubility (cont.)
If a sufficient amount of H
+
is added, (that is if the pH is
lowered even further), then:
H
+
(aq)
+ HCO
3
-
(aq)
H
2
CO
3(aq)
In conclusion, decreasing the pH results in the consumption
of CO
3
-2
.
Hence, decreasing the pH leads to a shift of the equilibrium
dissolution for CaCO
3
favoring further dissolution of the solid
CaCO
3
.
We say that decreasing the pH leads to an increase in the
solubility of CaCO
3
.
In general, If an ionic compound contains the anion of a
weak acid, the addition of a strong acid increases its
solubility.
Section 17.8: Predicting the Formation
of a Precipitate
In the chapter on Equilibrium, we learned about the
relationship between the reaction quotient, Q, and
the equilibrium constant, K.
The relationship between Q and K tells us the
direction in which a reaction must proceed for the
system to reach equilibrium.
The same approach is used here to discuss the
formation of a precipitate.
If Q and K are the reaction quotient and the
equilibrium constant, respectively, then Q
sp
and K
sp
are the solubility product quotient and the solubility
product constant, respectively.
of a Precipitate (cont.)
Let us consider the dissolution equilibrium for a
general ionic solid MX.
MX
(s)
M
+
(aq)
+ X
-
(aq)
When we refer to the saturatedaqueous solution
of an ionic compound, we imply that this solution is
at equilibrium.
The concentrations of M
+
and X
-
in the saturated
solution are the equilibrium concentrations, [M
+
]
(eq)
and [X
-
]
(eq)
.
If we call S, the molar solubility of MX, then, for a
saturated solution:
[M
+
]= [M
+
]
(eq)
= S and [X
-
] = [X
-
]
(eq)
= S
For a non-saturated solution, the ion
concentrations are:
[M
+
] [M
+
]
(eq)
and [X
-
] [X
-
]
(eq)
The solubility product quotient and constant are
then expressed as:
Q
sp
= [M
+
][X
-
] and K
sp
=[M
+
]
(eq)
[X
-
]
(eq)
= S
2
Hence, for a saturated solution Q
sp
=K
sp
(equilibrium
chemical system).
When the concentrations of ions in solution are such that
[M
+
][X
-
] > [M
+
]
eq
[X
-
]
eq
, that is Q
sp
>K
sp
, the solution is said
to be supersaturated.
The reaction proceeds in the direction in which M
+
(aq)
and
X
-
(aq)
are consumed and the precipitate MX
(s)
forms.
Hence, precipitation results in a decrease of the reaction
quotient, Q
sp
.
The precipitation continues until Q
sp
reaches its equilibrium
value, K
sp
. At this point, the solution becomes saturated
(Q
sp
=K
sp
).
When the concentrations of ions in solution are such that
[M
+
][X
-
] < [M
+
]
eq
[X
-
]
eq
, that is Q
sp
<K
sp
, the solution is said
to be unsaturated.
What happens depends on whether any solid MX is
present in solution.
Assuming some solid is present in solution:
The solid will dissolve, thereby increasing the
concentrations of M
+
and X
-
ions in solution and the
reaction quotient, Q
sp
.
The dissolution continues until Q
sp
reaches its equilibrium
value, K
sp
. At this point, the solution becomes saturated
(Q
sp
=K
sp
).
Assuming no solid is present in solution:
As no solid dissolves, the solution remains
unsaturated.

Chapter 17

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