Chem 17

Ch.
16 Practice:
What is the pH of a 0.085 M solution of aniline, C6H5NH2 (pKb = 9.37)?
What is the Ka of benzoic acid if a 0.15 M solution has a pH of 2.51?
Ch. 16 Practice:
What is the pH of a 0.085 M solution of aniline, C6H5NH2 (pKb = 9.37)?
[OH ] Kb [BOH]
Kb = 10-pKb = 10-9.37 = 4.2710-10
10
6
[OH ] (4.27 10 ) (0.085) 6.02 10
6.02 106
% ionization 0.085 100% 0.007%
pOH = -log(6.0210-6) = 5.22
pH = 14 pOH = 8.78
What is the Ka of benzoic acid if a 0.15 M solution has a pH of 2.51?
[H ][A- ]
K a [HA]
[H+] = 10-2.51 = 3.0910-3 M
[HA] = 0.15 3.0910-3 = 0.1469 M
Ka = (3.0910-3)2 / 0.1469 = 6.510-5
Chapter 17
Additional Aspects of
Aqueous Equilibria
As he that taketh away a garment in cold
weather, and as vinegar upon nitre, so is
he that singeth songs to an heavy heart.
Proverbs 25:20 (KJV)
The Common Ion Effect
17.1.1
Consider a solution of acetic acid in water.

CH3CO2H(aq) + H2O(l) H3O+(aq) + CH3CO2-(aq)
The equilibrium can be expressed by :
[H 3O ][CH 3CO-2]
K eq
[CH 3CO2 H]
If additional acetate ion was added to the solution, for example
by the addition of NaCH3CO2 (a strong electrolyte), this would
affect the dissociation of the acid by shifting the equilibrium to
the left, which will reduce the [H+] (increase the pH) of the
solution.
17.1.2
CH3CO2H(aq) + H2O(l) H3O+(aq) + CH3CO2-(aq)

Common-ion effect: The extent of ionization of a weak
electrolyte is decreased by adding to the solution a strong
electrolyte that has an ion in common with the weak electrolyte.
In agreement with Le Chteliers Principle: if a system at
equilibrium is disturbed, the system will move in such a way as
to counteract the disturbance.
The addition of the ion is the disturbance, and the system
responds by reducing the disturbance.
17.1.3
Example 1
What is the pH of a solution of 0.30 mol acetic acid and 0.30 mol
sodium acetate in 1.0 L solution
What is the significant reaction?
HCH3CO2(aq) + H2O(l) H3O+(aq) + CH3CO2-(aq)
What species are involved in the equilibrium
HCH3CO2(aq), H3O+(aq), CH3CO2-(aq)
What are the equilibrium concentrations of these species?
Init.
[HCH3CO2], M
0.30
Change
Equil.
-x
0.30 - x
[H3O+], M
0
+x
x
[CH3CO2-], M
0.30
+x
0.30 + x
17.1.4
Example 1
Init.
[HCH3CO2], M
0.30
[H3O+], M
0
[CH3CO2-], M
0.30
Change
Equil.
-x
0.30 - x
+x
x
+x
0.30 + x
[H 3O ][CH 3CO-2]
Ka
[HCH 3CO2 ]
(x)(0.30 x)
1.8 10
(0.30 x)
5
Ka is small, so we can assume x is small, and we can simplify the

expression and solve for x and pH:
( x)(0.30)
5
5
x
1.8
10
M
[H
]
1.8 10
(0.30)
pH log(1.8 105 ) 4.74
Example 1
17.1.5
What is the pH of a 0.30 M solution of acetic acid, without the

added acetate ion?
2
[H
O
][CH
CO
]
(
x
)
5
3
2
1.8 10 3
[HCH 3CO 2 ]
0.30
x = 2.310-3
pH = -log(2.310-3) = 2.64
The addition of a common ion (CH3CO2-) to a solution of a
weak electrolyte (HCH3CO2) reduced the ionization of the
HCH3CO2
(from 2.310-3 to 1.810-5 moles ionized per liter)
17.1.6
Example 2
What is the concentration of F- in a solution that is 0.20 M in HF

and 0.10 M in HCl?
What is the significant reaction?
HF(aq) + H2O(l) H3O+(aq) + F-(aq)
What species are involved in the equilibrium?
HF(aq), H3O+(aq), F-(aq)
What are the equilibrium concentrations of these species?
Init.
[HF], M
0.20
[H3O+], M
0.10
Change
Equil.
-x
0.20 - x
+x
0.10 + x
[F-], M
0
+x
x
17.1.7
Example 2
Init.
[HF], M
0.20
[H3O+], M
0.10
[F-], M
0
Change
Equil.
-x
0.20 - x
+x
0.10 + x
+x
x
[H 3O ][F - ]
Ka
[HF]
(0.10 x)(x)
6.8 10
(0.20 x)
4
We can assume x is small, and we can simplify the expression and

solve for x:
(0.10)(x)
6.8 10
(0.20)
4
x 1.4 103 M [F
[F]]
Example 2
17.1.8
What would the concentration of F- be without the presence of

the HCl?
2
[H
O
][F
]
(
x
)
2
4
3
x
1.2
10
M
[F
]
6.8 10
[HF]
0.20
We have added an ion (H3O+) common to the ionization of the
weak electrolyte (HF) and reduced the ionization of the HF
(from 1.210-2 to 1.410-3 moles ionized per liter)
17.1.9
This effect is not only for acids.

Weak bases also show this effect:
NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)
This reaction will be shifted to the left with the addition of a
strong electrolyte such as NH4Cl(aq).
This effect can also be seen in the solubility of salts.

The addition of HCl to a saturated solution of NaCl will cause
the precipitation of NaCl:
NaCl(s) Na+(aq) + Cl-(aq)
Buffered Solutions
17.2.1
Composition and Action of Buffered Solutions

A buffer consists of a mixture of a weak acid (HA) and its
conjugate base (A-):
HA(aq) + H2O(l) A-(aq) + H3O+(aq)
The Ka expression is:
[H ][A- ]
Ka
[HA]
Which can be solved for the [H+]:
[HA]
[H ] K a
[A- ]
Buffered Solutions
17.2.2

When a small amount of H+ is added to the buffer, A- is
consumed to produce HA. But, if the amount of HA and A- are
large compared to the amount of H+ added, the [HA]/[A-] ratio
does not change much, so the pH is not significantly changed.
A-(aq) + H3O+(aq) HA(aq) + H2O(l)
Buffered Solutions
17.2.3

When a small amount of OH- is added to the buffer, the OHreacts with HA to produce A- and water. Once again, the
[HA]/[A-] ratio does not change much, so the pH is not
significantly changed.
HA(aq) + OH- (aq) A-(aq) + H2O(l)
Buffered Solutions
17.2.4
Buffer Capacity
Buffer capacity is the amount of acid or base neutralized by the
buffer before there is a significant change in pH.
The pH of the solution depends on the Ka of the acid, and the
relative concentrations of the weak acid and its conjugate base.
Buffer capacity depends on the amount of the weak acid and its
conjugate base.
The greater the amounts of conjugate acid-base pair, the greater
the buffer capacity.
Buffered Solutions
17.2.5
Buffer Capacity and pH

Consider two solutions, one that is 1.0 M in each of HCH3CO2
and NaCH3CO2, and the other is 0.1 M in each.
The pH of both solutions will be the same.
[HA]
[H ] K a
[A- ]
But the buffering capacity of the 1.0 M solution will be greater,
because it contains more of the acid and conjugate base.
Buffered Solutions
17.2.6
Buffer Capacity and pH

The pH of a buffered solution can be calculated, if you know
the concentrations of the acid and the conj. base.
[HA]
[H ] K a
[A- ]
If the negative log of this equation is taken, we get the
Henderson-Hasselbach equation:
[HA]
log[H ] log K a log [A ]
[A - ]
p H pK a log
[HA]
Buffered Solutions
17.2.7
Addition of Strong Acids or Bases to Buffers

This breaks the calculation into two parts: stoichiometric and
equilibrium.
The amount of strong acid or base added results in a neutralization
reaction:
A- + H3O+ HA + H2O
HA + OH- A- + H2O
By knowing how much H3O+ or OH- was added (stoichiometry)
we know how much HA or A- is formed.
With the concentrations of HA and A-, the pH (equilibrium) can be
calculated from the Henderson-Hasselbalch equation.
Buffered Solutions
17.2.8
A buffer is prepared that is 0.100 M in each of HCH3CO2 and

NaCH3CO2.
Two beakers are prepared, each with 50.0 mL of buffer solution.
Two more beakers are prepared with 50.0 mL of water only.
A 5.00 mL aliquot of 0.100 M HCl is added to one of the buffers
and to one of the waters.
A 5.00 mL aliquot of 0.100 M NaOH is added to the other buffer
and to the other water.
What is the pH of the buffer, of the water, and the buffer and water
after the addition of the acid and the base?
17.2.9
Buffered Solutions
Buffer
Acid
Initial
Base
Water
Buffered Solutions
17.2.10
Calculate the number of moles of each species in each buffer

and aliquots (we will calculate concentration later).
Buffer:
mol(HCH3CO2) = (0.100 M)(0.0500 L) = 0.00500 mol
mol(CH3CO2-) = (0.100 M)(0.0500 L) = 0.00500 mol
Aliquots:
mol(H+) = (0.100 M)(0.00500 L) = 5.0010-4 mol
mol(OH-) = (0.100 M)(0.00500 L) = 5.0010-4 mol
Buffered Solutions
Calculate the pH of the buffer alone:
[HCH3CO3] = 0.00500 mol / 0.0500 L = 0.100 M
[CH3CO3-] = 0.100 M
[CH 3CO-2]
p H pK a log
[CH CO H]
3
0.100 M
p H log(1.80 10 ) log
0.100 M
5
p H 4.745 log(1)
p H 4.745
17.2.11
Buffered Solutions
17.2.12
Calculate the pH of the buffer with the added HCl:

HCH3CO2(aq) + H2O(l) CH3CO2-(aq) + H3O+(aq)
[HCH3CO2] = (0.00500 + 0.0005 mol)/0.0550 L = 0.100 M
[CH3CO-2] = (0.00500 - 0.0005 mol)/0.0550 L = 0.0818 M
[CH 3CO-2]
p H pK a log
[HCH CO ]
3
0.0818M
p H 4.745 log
0.100M
p H 4.745 0.0872 4.658
Buffered Solutions
17.2.13
Calculate the pH of the buffer with the added NaOH:

HCH3CO2(aq) + H2O(l) CH3CO2-(aq) + H3O+(aq)
[HCH3CO2] = (0.00500 - 0.0005 mol)/0.0550 L = 0.0818 M
[CH3CO2-] = (0.00500 + 0.0005 mol)/0.0550 L = 0.100 M
[CH 3CO-2]
p H pK a log
[HCH CO ]
3
0.100M
p H 4.745 log
0.0818M
p H 4.745 0.0872 4.832
Buffered Solutions
Calculate the pH of the water with the added HCl:
M = mol/L
M = 5.0010-4 mol/0.0550 L = 9.0910-3 M
pH = -log(9.0910-3) = 2.041
17.2.14
Buffered Solutions
Calculate the pH of the water with the added NaOH:
M = mol/L
M = 5.0010-4 mol/0.055 L = 9.0910-3 M
pOH = -log(9.0910-3) = 2.041
pH = 14 2.041 = 11.959
17.2.15
17.2.16
Buffered Solutions
Buffer
Water
Acid
4.658
2.041
Initial
4.745
7.000
Base
4.832
11.959
17.3.1
Acid-Base Titrations
Titration
In a titration, an unknown acid (for example) is neutralized with

a known quantity of a standard base.
If the pH of the solution is plotted versus the volume of base
added, it is called a titration curve.
Unknown HCl Titration
12.00
10.00
pH
8.00
6.00
4.00
2.00
0.00
0.00
5.00
10.00
15.00
Vol NaOH (mL)
20.00
25.00
17.3.2
Titration
As the base is added, it consumes a stoichiometric quantity of
the acid.
HA(aq) + BOH(aq) A-(aq) + B+(aq) + H2O(l)
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 point at which the color
change of the indicator occurs
The difference between equivalence point and end point is
called the titration error
17.3.3
Strong Acid-Strong Base Titrations

Before any base is added, the pH is given by the strong acid
solution. Therefore, pH < 7
When base is added, before the equivalence point, the pH is
given by the amount of strong acid in excess. Therefore, pH < 7
At the equivalence point, the amount of base added is
stoichiometrically equivalent to the amount of acid originally
present. Therefore, the pH is determined by the salt solution.
Therefore, pH = 7
If more base is added, the pH is given by the amount of strong
base in excess. Therefore, pH > 7
17.3.4
Strong Acid-Strong Base Titrations
Either phenolphthalein or methyl red would work as an

indicator, both change color in the steep portion of the curve.
Example
17.3.5
What is the pH of a solution of 50.0 mL of 0.100 M HCl when

49.0 mL of 0.100 M NaOH has been added?
How many moles of H+ were in the original solution?
(0.100 mol/L) (0.0500 L) = 5.0010-3 mol H+
How many moles of OH- were added?
(0.100 mol/L) (0.0490 L) = 4.9010-3 mol OH How many moles H+ remain?
5.0010-3 mol 4.9010-3 mol = 1.010-4 mol H+
What is the total volume of solution?
0.0500 L + 0.0490 L = 0.0990 L
What is the final [H+]?
(1.010-4 mol H+) / (0.0990) = 1.010-3 M
What is the pH?
pH = -log(1.010-3) = 3.00
Example
17.3.6
When 51.0 mL has been added?

How many moles of H+ were in the original solution?
(0.100 mol/L) (0.0500 L) = 5.0010-3 mol H+
(0.100 mol/L) (0.0510 L) = 5.1010-3 mol OH How many moles OH- remain?
5.1010-3 mol 5.0010-3 mol = 1.010-4 mol OH What is the total volume of solution?
0.0500 L + 0.0510 L = 0.101 L
What is the final [OH-]?
(1.010-4 mol OH-) / (0.101 L) = 9.910-4 M
What is the pH?
pOH = -log(9.910-4) = 3.00
pH = 11.00
Strong Base-Strong Acid Titrations
The shape of a strong basestrong acid titration curve is
very similar to a strong acidstrong base titration curve,
except that the pH starts
high, then decreases as the
titration progresses.
Either phenolphthalein or
methyl red would work as
an indicator.
17.3.7
Example
17.3.8
What is the pH of a solution when 24.9 mL of 0.10 M HBr has

been added to 25.0 mL of 0.10 M NaOH?
How many moles of OH- were in the original solution
(0.10 mol/L) (0.0250 L) = 2.5010-3 mol OH How many moles of H+ were added?
(0.10 mol/L) (0.0249 L) = 2.4910-3 mol H+
How many moles OH- remain?
2.5010-3 mol 2.4910-3 mol = 1.010-5 mol OH What is the total volume of solution?
0.0250 L + 0.0249 L = 0.0499 L
What is the final [OH-]?
(1.010-5 mol OH-) / (0.0499) = 2.010-4 M
What is the pH?
pOH = -log(2.010-4) = 3.70 pH = 10.30
Example
17.3.9
When 25.1 mL has been added?

How many moles of OH- were in the original solution?
(0.10 mol/L) (0.0250 L) = 2.5010-3 mol OH How many moles of H+ were added?
(0.10 mol/L) (0.0251 L) = 2.5110-3 mol H+
How many moles H+ remain?
2.5110-3 mol 2.5010-3 mol = 1.010-5 mol H+
0.0250 L + 0.0251 L = 0.0501 L
What is the final [H+]?
(1.010-5 mol H+) / (0.0501) = 2.010-4 M
What is the pH?
pH = -log(2.010-4) = 3.70
17.3.10
Weak Acid-Strong Base Titrations

Consider the titration of acetic acid, HC2H3O2 with NaOH
Before any base is added, the solution contains only weak acid.
Therefore, the pH can be calculated with the equilibrium
calculation
As strong base is added, the strong base consumes a
stoichiometric quantity of weak acid
HC2H3O2(aq) + NaOH(aq) Na+(aq) + C2H3O2-(aq) + H2O(l)
17.3.11

Before the equivalence point is reached, there is an excess of
the weak acid, and there is a mixture of the weak acid and its
conjugate base
The pH can be calculated at any point during the titration
First, the amount of HC2H3O2 remaining, and the amount of
C2H3O2- generated is calculated, using the starting
concentrations, the amount of base added, and the
stoichiometry
Then the pH is calculated using either the equilibrium
expression or the Henderson-Hasselbalch equation
Example
17.3.12
What is the pH of a solution of 50.0 mL of 0.100 M HC2H3O2

(Ka = 1.810-5) when 45.0 mL of 0.100 M NaOH has been added?
How many moles of HC2H3O2 in the original solution
(0.100 mol/L) (0.0500 L) = 5.0010-3 mol HC2H3O2
(0.100 mol/L) (0.0450 L) = 4.5010-3 mol OH How many moles HC2H3O2 remain?
5.0010-3 mol 4.5010-3 mol = 5.010-4 mol HC2H3O2
How many moles C2H3O2- are formed?
4.510-3 mol C2H3O2-
Example
17.3.13

0.0500 L + 0.0450 L = 0.0950 L
What is the final [HC2H3O2]?
[HC2H3O2] = (5.010-4 mol) / (0.0950 L) = 5.310-3 M
What is the final [C2H3O2-]?
[C2H3O2-] = (4.510-3 mol) / (0.0950 L) = 4.710-2 M
Example
17.3.14
Now we can use the equilibrium expression to calculate [H+]

and pH
[HC2 H 3O 2 ]
[H ] K a
[C2 H 3O 2 ]
3
(5.3
10
)
5
[H ] 1.8 10
(4.7 102 )
[H+] = 2.010-6
pH= -log(2.010-6) = 5.70
17.3.15
Notice that methyl red would be a poor choice for an indicator

for this titration, the color change (end point) would occur well
before the equivalence point.
Phenolphthalein would be a much better choice.
17.3.16

At the equivalence point, all of the acetic acid, HC2H3O2, and
all of the NaOH has been consumed. However, C2H3O2- has
been generated and is still in solution.
Therefore, the pH is given by the C2H3O2- in solution.
This means pH > 7 at the equivalence point.
The pH at the equivalence point is determined by the Kb of the
conjugate base.
After the equivalence point, the pH is given by the strong base
in excess.
17.3.17

The titration curves for a weak acid-strong base titration differs
from a titration curve of a strong acid-strong base titration in
three important ways.
The initial pH is higher for a weak acid than for a strong
acid, for solutions of the same concentration.
The pH change on the steep portion of the curve is smaller
for a weak acid than for a strong acid.
The pH of the equivalence point is higher for a weak acid
than for a strong acid.
17.3.18

Acids Titrated with a Strong Base
14
12
10
pKa
8
pH
0
2
6
4
6
8
0
0.00
0.25
0.50
0.75
1.00
Fraction of Equivalence Point
1.25
However, the shape of the

curves after the
equivalence point is the
same because pH is
determined here by the
concentration of the
strong base in excess.
Example
17.3.19
What is the pH of a solution of 40.0 mL of 0.0250 M benzoic acid

(HC7H5O2, Ka = 6.310-5) when 5.0 mL of 0.050 M NaOH has been
added?
(0.0250 mol/L) (0.0400 L) = 1.0010-3 mol HC7H5O2
1.0010-3 mol 2.510-4 mol = 7.510-4 mol HC7H5O2
2.510-4 mol C7H5O2-
Example
17.3.20

0.0400 L + 0.0050 L = 0.0450 L
[HC7H5O2] = (7.510-4 mol) / (0.0450 L) = 1.710-2 M
[C7H5O2-] = (2.510-4 mol) / (0.0450 L) = 5.610-3 M
Using the equilibrium expression to calculate [H+]
[HC7 H 5O 2 ]
[H ] K a
[C7 H 5O 2 ]
2
5 (1.7 10 )
4
[H ] 6.3 10
1.9
10
M
3
(5.6 10 )
pH log(1.9 104 ) 3.72
Example
17.3.21
When 15.0 mL NaOH has been added?

(0.0250 mol/L) (0.0400 L) = 1.0010-3 mol HC7H5O2
1.0010-3 mol 7.510-4 mol = 2.510-4 mol HC7H5O2
7.510-4 mol C7H5O2-
Example
17.3.22

0.0400 L + 0.0150 L = 0.0550 L
[HC7H5O2] = (2.510-4 mol) / (0.0550 L) = 4.510-3 M
[C7H5O2-] = (7.510-4 mol) / (0.0550 L) = 1.410-2 M
Using the equilibrium expression to calculate [H+]
[HC7 H 5O 2 ]
[H ] K a
[C7 H 5O 2 ]
3
5 (4.5 10 )
5
[H ] 6.3 10
2.1
10
M
2
(1.4 10 )
pH log(2.1105 ) 4.68
Example
17.3.23

(0.0250 mol/L) (0.0400 L) = 1.0010-3 mol HC7H5O2
1.0010-3 mol 1.0010-3 mol = 0.00 mol HC7H5O2
The acid has been exactly neutralized, so the pH depends only on the
concentration of the conjugate base
1.0010-3 mol C7H5O2-
Example
17.3.24

0.0400 L + 0.0200 L = 0.0600 L
[C7H5O2-] = (1.0010-3 mol) / (0.060 L) = 1.710-2 M
What is the Kb for the conjugate base?
Kb = Kw/Ka = 1.0010-14/6.310-5 = 1.610-10
What is [OH-] and pH?
[OH ] K b [A ]
[OH ] (1.6 1010 ) (1.7 102 ) 1.6 106

pOH 5.79
pH = 8.21
Example
17.3.25

(0.0250 mol/L) (0.0400 L) = 1.0010-3 mol HC7H5O2
(0.0500 mol/L) (0.0250 L) = 1.2510-3 mol OH How many moles OH- remain?
1.2510-3 mol 1.0010-3 mol = 2.510-4 mol OH The acid has been more than neutralized, so the pH depends only on
the concentration of the strong base remaining
0.0400 L + 0.0250 L = 0.0650 L
Example
What is the final [OH-] and pH?
[OH-] = (2.510-4 mol) / (0.0650 L) = 3.810-3 M
pOH = 2.41, pH = 11.59
17.3.26
17.3.27
Weak Base-Strong Acid Titrations

The titration of a weak base with a strong acid follows the same
process as a weak acid-strong base titration, except the pH starts
high and decreases during the titration.
17.3.28
Weak Base-Strong Acid Titrations
Notice that phenolphthalein would be a poor choice for an

indicator for this titration, the color change (end point) would
occur well before the equivalence point.
Methyl red would be a much better choice.
Practice
17.3.29
What is the pH when 10.0 mL of 0.095 M HCl has been added to

20.0 mL of 0.100 M NH3 (Kb = 1.810-5)?
When 21.05 mL HCl has been added?
Practice
17.3.29a
What is the pH when 10.0 mL of 0.095 M HCl has been added to

20.0 mL of 0.100 M NH3 (Kb = 1.810-5)?
How many moles of NH3 were in the original solution?
(0.100 mol/L) (0.0200 L) = 2.0010-3 mol NH3
How many moles of H+ were added?
(0.095 mol/L) (0.0100 L) = 9.510-4 mol H+
How many moles NH3 remain?
2.0010-3 mol 9.510-4 mol = 1.0510-3 mol NH3
How many moles NH4+ are formed?
9.510-4 mol NH4+
0.0200 L + 0.0100 L = 0.0300 L
Practice
17.3.29b
What is the final [NH3]?

[NH3] = (1.0510-3 mol) / (0.0300 L) = 3.5010-2 M
What is the final [NH4+]?
[NH4+] = (9.510-4 mol) / (0.0300 L) = 3.210-2 M
Using the equilibrium expression to calculate [OH-]
[OH ][NH 4 ]
Kb
[NH 3 ]
2
[OH
](3.2
10
)
5
1.8 10
(3.50 102 )
[OH ] 2.0 105 M
pOH log(2.0 105 ) 4.70

pH 9.30
Practice
(0.100 mol/L) (0.0200 L) = 2.0010-3 mol NH3
(0.095 mol/L) (0.02105 L) = 2.0010-3 mol H+
How many moles NH3 remain?
2.0010-3 mol - 2.0010-3 mol = 0.00 mol
How many moles NH4+ are formed?
2.0010-3 mol NH4+
0.0200 L + 0.02105 L = 0.0410 L
17.3.29c
Practice
17.3.29d
What is the final [NH4+]?

[NH4+] = (2.0010-3 mol) / (0.0410 L) = 4.8710-2 M
What is the Ka for the conjugate acid?
Ka = Kw/Kb = 1.0010-14/1.810-5 = 5.610-10
What is [H+] and pH?
[H ] K a [HA]
6
[H ] (5.6 1010 ) (4.87 10 2 ) 5.2 10 M
pH 5.28
Practice
(0.100 mol/L) (0.0200 L) = 2.0010-3 mol NH3
(0.095 mol/L) (0.0300 L) = 2.8510-3 mol H+
How many moles H+ are excess?
2.8510-3 mol - 2.0010-3 mol = 8.510-4 mol
0.0200 L + 0.0300 L = 0.0500 L
What is the final [H+] and pH?
[H+] = (8.510-4 mol) / (0.0500 L) = 1.710-2 M
pH = 1.77
17.3.29e
17.3.30
Weak Acid-Weak Base Titrations

Not normally considered, as it is too difficult to accurately
determine the equivalence point in the titration
17.3.31
Unknown Acid Titrations

What do you do if you have a solution that contains an acid, but
you do not know if it is strong or weak?
Titrate it with a strong base
Use phenolphthalein as an indicator
17.3.32
Unknown Base Titrations

What do you do if you have a solution that contains a base, but
you do not know if it is strong or weak?
Titrate it with a strong acid
Use methyl red as an indicator
Solubility Equilibria
17.4.1
The Solubility-Product Constant, Ksp

We have been dealing with homogeneous equilibria, that is, all
species are in the same phase
HC2H3O2(aq) H+(aq) + C2H3O2-(aq)
Equilibria can also be heterogeneous, such as saturated aqueous

salt solutions
A saturated solution is one in which the dissolved solute is in
equilibrium with the undissolved solid
NaCl(s) Na+(aq) + Cl-(aq)
17.4.2

Consider
BaSO4(s) Ba2+(aq) + SO42-(aq)
for which
Ksp = [Ba2+][SO42-]
Ksp is the solubility product

Remember, [BaSO4(s)] is ignored in the equilibrium
expression because it is a pure solid so its concentration is
constant as long as some solid remains.
17.4.3

In general: the solubility product of a substance is the molar
concentration of the ions in a saturated solution raised to their
stoichiometric powers.
The solubility of a substance is the amount (in grams) of the
substance that dissolves to form a liter of saturated solution. Units
are usually expressed as g/L
Can also be expressed as g/100mL (watch your units)
Molar solubility is the number of moles of solute dissolving to
form a liter of saturated solution
17.4.4
Ksp , solubility, and molar solubility all give us the same

information, just expressed differently:
Ksp is the concentration of the ions of an ionic solid in a
saturated solution raised to the power of the ions
stoichiometry, and is constant at constant T
Solubility is the concentration of the ions of an ionic solid in
a saturated solution given in grams of the salt per liter
Molar solubility is the concentration of the ions of an ionic
solid in a saturated solution given in moles of the salt per
liter
17.4.5
Solubility and Ksp

To convert solubility to Ksp
If needed, convert solubility into molar solubility
(via molar mass)
convert molar solubility into the molar concentration of ions at
equilibrium (via stoichiometry)
Ksp is the product of equilibrium concentration of ions raised to the
power of their stoichiometry
Example
17.4.6
The molar solubility of PbBr2 is 1.010-2 mol/L at 25 C.

What is its Ksp?
PbBr2(s) Pb2+(aq) + 2 Br-(aq)
Ksp = [Pb2+][Br-]2
[Pb2+] = 1.010-2 M
[Br-] = 2(1.010-2 M) = 2.010-2 M
Ksp = (1.010-2)(2.010-2)2
Ksp = 4.010-6
17.4.7
Example
The solubility of Ag2CrO4 is 2.110-3 g/100 mL at 25 C.

What is the Ksp?
Ag2CrO4(s) 2 Ag+(aq) + CrO42-(aq)
2.1103g 1000 mL
100 mL
1L
mol
331.73 g
6.3 105 M
Ksp = [Ag+]2[CrO42-]
[CrO42-] = 6.310-5 M
[Ag+] = 2(6.310-5) = 1.310-4 M
Ksp = (1.310-4)2 (6.310-5)
Ksp = 1.010-12
17.4.8
Solubility and Ksp

To convert Ksp to solubility
write the equilibrium expression, using x for the
concentration of the ions (dont forget the exponents)
solve for x, convert x to molarity of salt
If needed, convert molarity to grams per liter using the molar
mass of the salt
Example
17.4.9
The Ksp of CaF2 is 3.910-11 at 25 C. What is the solubility of

CaF2 in g/L?
CaF2(s) Ca2+(aq) + 2 F-(aq)
Let x = [Ca2+] , [F-] = 2x

Ksp = [Ca2+][F-]2
3.910-11 = (x)(2x)2 = 4x3
x = 2.110-4 M = [Ca2+]
If [Ca2+] = 2.110-4 M, then 2.110-4 mol CaF2 dissolves in
one liter of solution
2.1 10 4 mol 78.075 g

L
mol
1.7 10 2 g/L
Example
17.4.10
A saturated solution of Mg(OH)2 has a pH of 10.52 at 25 C.

What is the Ksp?
Mg(OH)2(s) Mg2+(aq) + 2 OH-(aq)
Ksp = [Mg2+][OH-]2
[H+] = 10-10.52 = 3.0210-11
[OH-] = 10-14 / 3.0210-11 = 3.3110-4 M
[Mg2+] = [OH-] = 1.6610-4 M
Ksp = (1.6610-4)(3.3110-4)2
Ksp = 1.810-11
Factors that Affect Solubility
17.5.1

We have already looked at the common ion effect, an
application of Le Chteliers principle:
When Ca2+ is added (e.g., from Ca(NO3)2), the equilibrium
shifts away from the increase
Therefore, CaF2 is less soluble in a solution that already
contains some Ca2+
Example
17.5.2
What is the molar solubility of CaF2 in a solution that is 0.010

M in Ca(NO3)2? Ksp of CaF2 = 3.910-11
Ksp = [Ca2+][F-]2
Let x = moles of CaF2 that dissolves in 1 liter
[Ca2+] = (0.010 + x) M
[F-] = 2x
3.910-11 = (0.010 + x)(2x)2
3.910-11 = (0.010)(2x)2
0.040x2 = 3.910-11
x = 3.110-5 moles of CaF2 would dissolve in 1 L
Without the added Ca2+, the solubility was 2.110-4 mol/L
17.5.3
Solubility and pH
Lets look at another aspect of Le Chteliers principle:
If Ca2+ is added, then the equilibrium shifts away from the
increase and CaF2 precipitates
The equilibrium can also be shifted the other direction
F- can be removed by adding a strong acid:
F-(aq) + H+(aq) HF(aq)
As pH decreases, [H+] increases and solubility increases, and
the effect can be dramatic
Example
17.5.4
What is the molar solubility of Mg(OH)2 in a solution buffered

at pH = 9.52? Ksp of Mg(OH)2 = 1.810-11
Mg(OH)2(s) Mg2+(aq) + 2 OH-(aq)
Ksp = [Mg2+][OH-]2
[H+] = 10-9.52 = 3.0210-10 M
[OH-] = 10-14 / 3.0210-10 = 3.3110-5 M
Let x = moles of Mg(OH)2 that dissolves in 1 liter
[Mg2+] = x M
[OH-] = 3.3110-5 M
1.810-11 = (x)(3.3110-5)2
x = 0.017 moles of Mg(OH)2 would dissolve per liter
17.5.5
Solubility and pH
When Mg(OH)2 dissolves in water, the solubility was 1.710-4
M, and the resulting solution has a pH of 10.52 (slide 17.4.10)
A decrease of one pH unit, to pH = 9.52, increased the
solubility by a factor of 100, to 0.017 M
Mg(OH)2 works as an over-the-counter antacid, even though it
is insoluble
Due to the lower concentration of OH- at a lower pH, more
Mg(OH)2 dissolves, releasing more OH- to neutralize the
acid
Cleopatras Needle
Originally erected in the
Egyptian city of Heliopolis,
around 1450 BC
(Cleopatra lived over a
thousand years later)
224 tons of red granite
Moved to New York,
erected in Central Park
on February 22, 1881
Has been deteriorating
because of the acidic rain in
New York
17.5.6
17.5.7
Formation of Complex Ions

Metals are Lewis acids, accepting electron pairs to fill empty
orbitals. This effect will increase the solubility of the metal salt,
if a Lewis base is available.
Consider the formation of Ag(NH3)2+:
Ag+(aq) + 2 NH3(aq) Ag(NH3)2+(aq)
The Ag(NH3)2+ is called a complex ion

The complexed Lewis base is called a ligand
The Keq for the formation reaction is called the formation
constant, Kf
[Ag(NH 3 )2 ]
Kf
[Ag ][NH 3 ]2
17.5.8

Consider the addition of ammonia to AgCl (white solid):
AgCl(s) Ag+(aq) + Cl-(aq)
Ag+(aq) + 2 NH3(aq) Ag(NH3)2+(aq)
The overall reaction is
AgCl(s) + 2 NH3(aq) Ag(NH3)2+(aq) + Cl-(aq)
The Kf is 1.7107, favoring the formation of products, and
effectively removing the Ag+(aq) from solution.
Therefore, by Le Chteliers principle, more of the AgCl will
dissolve.
17.5.9

AgCl(s) Ag+(aq) + Cl-(aq)
Ksp= 1.810-10
Ag+(aq) + 2NH3(aq) Ag(NH3)2+(aq)
Kf = 1.7107
AgCl(s) + 2NH3(aq) Ag(NH3)2+(aq) + Cl-(aq)
Keq = (1.7107)(1.810-10) = 3.110-3

The stability of the complex ion in solution can be judged by
the formation constant of the complex ion from the metal ion

17.5.10
Precipitation and
Separation of Ions
17.6.1
Equilibrium can be reached starting from either side of an

equation:
BaSO4(s) Ba2+(aq) + SO42-(aq)
If we place some solid BaSO4 in water, the BaSO4 will dissolve
until the concentration of ions in solution reaches equilibrium,
Ksp = 1.110-10
Likewise, if we mix a solution that contains Ba2+ ions with a
solution that contains SO42- ions, if the overall concentration is
higher than equilibrium, BaSO4 will precipitate until
equilibrium is reached.
Precipitation and
Separation of Ions
17.6.2
At any instant in time, Q = [Ba2+][SO42-].

If Q > Ksp, precipitation occurs until Q = Ksp
If Q = Ksp, equilibrium exists
If Q < Ksp, solid dissolves until Q = Ksp
Using this phenomena, ions can be selectively removed from
solutions, based on the solubility of their salts
Precipitation and
Separation of Ions
17.6.3
Example
Will a precipitate form when 0.10 L of 8.010-3 M Pb(NO3)2 is
added to 0.40 L of 5.010-3 M Na2SO4?
Which salts are possible precipitates?
Metathesis products:
Pb(NO3)2(aq) + Na2SO4(aq) PbSO4(?) + 2 NaNO3(?)
NaNO3 is soluble, so only PbSO4
Calculate concentration of these ions (0.5 L total volume):
Pb2+: (8.010-3 M)(0.10 L)/(0.50L) = 1.610-3 M Pb2+
SO42-: (5.010-3 M)(0.40 L)/(0.50L) = 4.010-3 M SO42-
Precipitation and
Separation of Ions
Example
Now solve for Q, and compare it to the Ksp:
Q = [Pb2+][SO42-]
= (1.610-3 M)(4.010-3 M)
= 6.410-6
The Ksp of PbSO4 is 6.310-7
Since Q > Ksp, the salt will precipitate
17.6.4
Precipitation and
Separation of Ions
17.6.5
Consider a mixture of equal amounts of Zn2+(aq) and Cu2+(aq).

If a solution containing S2-(aq) is added, one or both of these
cations could form a precipitate.
ZnS (Ksp = 210-25)
CuS (Ksp = 610-37) less soluble
As H2S is added to the green solution, black CuS forms, leaving
a colorless solution of Zn2+(aq)
Cu2+(aq, green) + S2-(aq) CuS(s, black)
When more H2S is added, a second precipitate of white ZnS
forms
Zn2+(aq, colorless) + S2-(aq) ZnS(s, white)
Example
17.6.6
A solution contains 1.010-2 M Ag+ and 2.010-2 M Pb2+.

The Ksp of AgCl is 1.810-10 and the Ksp of PbCl2 is 1.710-5.
What concentration of Cl- is necessary to begin the precipitation
of each salt?
For AgCl, Ksp = [Ag+][Cl-]
1.810-10 = (1.010-2)[Cl-]
[Cl-] = 1.8 10-8 M
For PbCl2, Ksp = [Pb2+][Cl-]2:
1.710-5 = (2.010-2)[Cl-]2
[Cl-] = 2.910-2 M
A smaller concentration of Cl- is required to precipitate the Ag+
than the Pb2+
The Ag+ will precipitate first
Precipitation and
Separation of Ions
17.6.7
Selective Precipitation of Ions

If HCl is added to a solution containing Ag+ and Cu2+,
(Ksp(AgCl) = 1.810-10 and Ksp(CuCl2) = 5.6102)
the AgCl precipitates and the Cu2+ remains in solution.
Removal of one metal ion from a solution is called selective
precipitation.
This property can be used to separate and identify metals in a
solution
Qualitative Analysis for

Metallic Elements
17.7.1
Qualitative analysis is designed to detect the presence of a

substance.
Asks What is it? or Is it there?
Quantitative analysis is designed to determine how much of a
substance is present.
Asks How much is there?

Metallic Elements
17.7.2
We can separate a complicated mixture of ions into five groups

(a qualitative analysis):
Group 1: Insoluble chlorides
Add 6 M HCl to the mixture of cations to precipitate the
insoluble chlorides: AgCl, Hg2Cl2, and PbCl2
Group 2: Acid-insoluble sulfides

Filter off the precipitate. To the remaining mixture of
cations, add H2S in 0.2 M HCl to remove the acid insoluble
sulfides: CuS, Bi2S3, CdS, As2S3, Sb2S3, SnS2 (Note: PbS
and HgS are also insoluble).

Metallic Elements
17.7.3
Group 3: Base-insoluble sulfides and hydroxides

Filter off the precipitate. To the remaining mixture of
cations, add (NH4)2S at pH 8 to remove base insoluble
sulfides and hydroxides: Al(OH)3, Cr(OH)3, Fe(OH)3, ZnS,
NiS, CoS, MnS
Group 4: Insoluble phosphates

Filter off the ppt. To the remaining mixture, add
(NH4)2HPO4 to remove the insoluble phosphates:
MgNH4PO4, Ca3(PO4)2, Sr3(PO4)2, Ba3(PO4)2
Group 5: Solubles
The final mixture of cations contains the soluble cations: the
alkali metal cations and NH4+
17.7.4

Metallic Elements
17.7.5
Further analysis can be done on the precipitates to separate the ions

in each group:
In Group 1, if the ppt is treated with NH3, the AgCl will dissolve,
but the PbCl2 and the Hg2Cl2 will not.
AgCl(s) + 2 NH3(aq) Ag(NH3)2+(aq) + Cl-(aq)
We dont know if there is silver ion in the solution, so the
remaining precipitate is filtered off, and HCl is again added to
the solution
If Ag is present, it will precipitate once again as AgCl.
Ag(NH3)2+(aq) + Cl-(aq) + 2H+(aq) AgCl(s) + 2NH4+(aq)
Read Chapter 17
Chapter 17 Homework
Due: Friday, February 28

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Ch.

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