5 (II) - Ionic Equilibria-Acid Bes

Chapter 18
Ionic Equilibria: Acids and Bases
1
Chapter Goals
1. A Review of Strong Electrolytes

2. The Autoionization of Water
3. The pH and pOH Scales
4. Ionization Constants for Weak Monoprotic Acids
and Bases
5. Polyprotic Acids
6. Solvolysis
7. Salts of Strong Bases and Strong Acids
2
Chapter Goals
8. Salts of Strong Bases and Weak Acids

9. Salts of Weak Bases and Strong Acids
10. Salts of Weak Bases and Weak Acids
11. Salts That Contain Small, Highly Charged
Cations
3
A Review of Strong
Electrolytes
This chapter details the equilibria of weak acids

and bases.
We must distinguish weak acids and bases from strong
electrolytes.
Weak acids and bases ionize or dissociate
partially, much less than 100%.
In this chapter we will see that it is often less than 10%!
Strong electrolytes ionize or dissociate
completely.
Strong electrolytes approach 100% dissociation in
aqueous solutions.
4
A Review of Strong
Electrolytes
There are three classes of strong electrolytes.
1 Strong Water Soluble Acids
Remember the list of strong acids from Chapter 4.
100%
HNO3( ) H 2 O ( ) H 3O (aq) NO 3(aq)
or
100%
HNO3( ) H (aq) NO 3(aq)
5
A Review of Strong
Electrolytes 100%
HNO3( ) H 2 O ( ) H 3O (aq) NO 3(aq)
or
100%
HNO3( ) H (aq) NO 3(aq)
6
A Review of Strong
Electrolytes
2 Strong Water Soluble Bases
The entire list of these bases was also introduced in
Chapter 4.
H 2 O 100%
KOH (s) K (aq) OH -
(aq)
H 2 O 100% 2
Sr(OH) 2(s) Sr (aq) 2 OH -
(aq)
7
A Review of Strong
Electrolytes
3 Most Water Soluble Salts
The solubility guidelines from Chapter 4 will help you remember
these salts.
H 2 O 100%
NaCl (s) Na (aq) Cl -
(aq)
H 2 O 100% 2
Ca(NO3 ) 2 s Ca (aq) 2 NO 3(aq)
8
A Review of Strong
Electrolytes
The calculation of ion concentrations in solutions of
strong electrolytes is easy.
Example 18-1: Calculate the concentrations of ions
in 0.050 M nitric acid, HNO3.

HNO 3( ) H 2 O ( ) 100%
H 3O (aq) NO 3(aq)
0.050 M 0.050 M 0.050 M
9
A Review of Strong
Electrolytes
Example 18-2: Calculate the concentrations of ions
in 0.020 M strontium hydroxide, Sr(OH)2, solution.
You do it!
2
Sr(OH) 2(s) Sr
H 2O
(aq) 2 OH -
(aq)
0.020 M 0.020M 2 0.020M

0.040M
10
The Autoionization of Water
Pure water ionizes very slightly.
The concentration of the ionized water is less than one-
millionth molar at room temperature.
11
We can write the autoionization of water as a dissociation
reaction similar to those previously done in this chapter.
H 2 O ( )
H 2 O ( ) H 3O (aq) OH (aq)
-
Because the activity of pure water is 1, the
OH
equilibrium constant for this reaction is:
+
Kc H 3O
12
Experimental measurements have determined that
the concentration of each ion is 1.0 x 10 -7 M at 25oC.
Note that this is at 25oC, not every temperature!
We can determine the value of K c from this
information.

Kc H 3O OH
+
1.0 x 10 1.0 x 10
-7 -7
14
1.0 x10
13
This particular equilibrium constant is called the ion-
product for water and given the symbol Kw.
Kw is one of the recurring expressions for the remainder of
this chapter and Chapters 19 and 20.
K w H 3O +
OH
14
1.0 x10
14
Example 18-3: Calculate the concentrations of
H3O+ and OH- in 0.050 M HCl.
HCl + H 2 O H 3O + Cl
0.050M 0.050 M 0.050 M

Thus the H 3O 0.050 M .
+

The H 3O + and K w will allow us to calculate [OH - ].
15
Use the [H3O+] and Kw to determine the [OH-].
You do it!
H O OH 1.0 10
3
+ 14
OH H O 5.0 10
14 14
1.0 10 1.0 10
+ 2
3
OH 2.0 10 M
13
16
The increase in [H3O+] from HCl shifts the equilibrium
and decreases the [OH-].
Remember from Chapter 17, increasing the product
concentration, [H3O+], causes the equilibrium to shift to the
reactant side.
This will decrease the [OH-] because it is a product!
The [H 3O ] from HCl is 0.050 M
H 2O H 2O H O OH -
3
The [H 3O ] from K w is 2.0 10 -13 M .

The overall [H 3O ] 0.050 2.0 10-13 M 0.050 M .
17
Now that we know the [H3O+] we can calculate the
[OH-].
You do it!
K w [H 3O ][OH-] 1 10-14
Since [H 3O ] 0.050 M .
1 10 -14
[OH - ]
[H 3O ]
1 10 -14
[OH - ]
[0.050 M ]
[OH - ] 2.0 10 13 M
18
The pH and pOH scales
A convenient way to express the acidity and basicity
of a solution is the pH and pOH scales.
The pH of an aqueous solution is defined as:
+
pH = -log H 3O
19
In general, a lower case p before a symbol is read
as the negative logarithm of the symbol.
Thus we can write the following notations.

pOH = -log OH -
pAg = -log Ag +
and so forth for other quantities.
20
If either the [H3O+] or [OH-] is known, the pH and pOH can be calculated.
Example 18-4: Calculate the pH of a solution in which the [H 3O+] =0.030 M.
pH = -log H 3O +

pH log 3.0 10 2

pH 1.52
21
Example 18-5: The pH of a solution is 4.597. What
is the concentration of H3O+?
You do it!
pH -log[H3O ]
4.597 -log[H3O ]

log[H3O ] -4.597
[H 3O ] 10-4.597
5
[H 3O ] 2.53 10 M
22
A convenient relationship between pH and pOH may
be derived for all dilute aqueous solutions at 250C.
14
[H 3O ][OH ] 1.0 10
Taking the logarithm of both sides of this equation
gives:

log H 3O log OH
14.00
23
Multiplying both sides of this equation by -1 gives:

- log H 3O log OH
14.00
Which can be rearranged to this form:
pH pOH 14.00
24
Remember these two expressions!!
They are key to the next three chapters!
H O OH 1.0 10
3
14
pH pOH 14.00
25
The usual range for the pH scale is 0 to 14.
H O 1.0 M to H O 1.0 10
3

3
14
M
pH 0 to pH 14.00
And for pOH the scale is also 0 to 14 but
inverted from pH.
pH = 0 has a pOH = 14 and pH = 14 has a pOH = 0.
OH 1.0 10
14

M up to OH 1.0M

pOH 14.00 pOH 0
26
Example 18-6: Calculate the [H3O+], pH, [OH-], and
pOH for a 0.020 M HNO3 solution.
Is HNO3 a weak or strong acid?
What is the [H3O+] ?
HNO 3 H 2 O 100%
H 3O NO 3-
0.020 M 0.020 M 0.020 M
H O 2.0 10 M
3
2
pH -log 2.0 10 M 2
pH 1.70
27
Example 18-6: Calculate the [H3O+], pH, [OH-], and
pOH for a 0.020 M HNO3 solution.

K w H 3O OH 1.0 10 14
OH H O 2.0 10 5.0 10
14 14
1.0 10 1.0 10 13
2
M
3
pOH log5.0 10 12.30

13
28
To help develop familiarity with the pH and pOH scale we can
look at a series of solutions in which [H3O+] varies between 1.0
M and 1.0 x 10-14 M.
[H3O+] [OH-] pH pOH

1.0 M 1.0 x 10-14 M 0.00 14.00
1.0 x 10-3 M 1.0 x 10-11 M 3.00 11.00
1.0 x 10-7 M 1.0 x 10-7 M 7.00 7.00
2.0 x 10-12 M 5.0 x 10-3 M 11.70 2.30
1.0 x 10-14 M 1.0 M 14.00 0.00
29
Ionization Constants for
Weak Monoprotic Acids and
Bases
Lets look at the dissolution of acetic acid, a weak
acid, in water as an example.
The equation for the ionization of acetic acid is:

CH 3COOH H 2 O H 3O CH 3COO -
The equilibrium constant for this ionization is

expressed as:
Kc
H O CH COO
3

3

CH 3COOH H 2O
31
Bases
The water concentration in dilute aqueous solutions
is very high.
1 L of water contains 55.5 moles of water.
Thus in dilute aqueous solutions:
H 2O 55.5M
32
Bases
The water concentration is many orders of
magnitude greater than the ion concentrations.

Thus the water concentration is essentially that of
pure water.
Recall that the activity of pure water is 1.
K H O
H O CH COO
3

3

c 2
CH 3COOH
K
H O CH COO
3

3

CH 3COOH
33
Bases
We can define a new equilibrium constant for weak
acid equilibria that uses the previous definition.

This equilibrium constant is called the acid ionization
constant.
The symbol for the ionization constant is Ka.
Ka
H O CH COO
3

1.8 10
3

5
CH 3COOH
for acetic acid
34
Bases
In simplified form the dissociation equation and
acid ionization expression are written as:

CH 3COOH H CH 3COO -
Ka
H CH COO

3

1.8 10 5
CH 3COOH
35
Bases
The ionization constant values for several acids are
given below.
Which acid is the strongest?
Acid Formula Ka value
Acetic CH3COOH 1.8 x 10-5
Nitrous HNO2 4.5 x 10-4
Hydrofluoric HF 7.2 x 10-4
Hypochlorous HClO 3.5 x 10-8
Hydrocyanic HCN 4.0 x 10-10
36
Bases
From the above table we see that the order of
increasing acid strength for these weak acids is:

HF > HNO 2 > CH 3COOH > HClO > HCN
The order of increasing base strength of the anions
(conjugate bases) of these acids is:
- - - - -
F < NO < CH 3COO < ClO < CN
2
37
Bases
Example 18-8: Write the equation for the ionization
of the weak acid HCN and the expression for its

ionization constant.

HCN H CN -
Ka
H CN
-
4.0 x 10 -10
HCN
38
Ionization Constants for Weak
Monoprotic Acids and Bases
Example 18-9: In a 0.12 M solution of a weak
monoprotic acid, HY, the acid is 5.0% ionized.
Calculate the ionization constant for the weak acid.
You do it!
+
HY H + Y -
Ka
H Y
+ -
HY
39
Since the weak acid is 5.0% ionized, it is also 95% unionized.
Calculate the concentration of all species in solution.
H Y 0.05(0.12M ) 0.0060M
+
H Y 6.0 10 M
+ 3
HY 0.95(0.12M ) 0.11M
40
Use the concentrations that were just determined in the
ionization constant expression to get the value of Ka.
Ka
H Y

HY
Ka
6.0 10 6.0 10
3 3
0.11
4
K a 3.3 10
41
Example 18-10: The pH of a 0.10 M solution of a
weak monoprotic acid, HA, is found to be 2.97.
What is the value for its ionization constant?
pH = 2.97 so [H+]= 10-pH
H 10
2.97
H 1.110
3
M
42
Use the [H3O+] and the ionization reaction to
determine concentrations of all species.
HA H+ A-

Equil. []'s 0.10 - 1.1 10-3 1.1 10-3 1.1 10-3
0.10
43
Calculate the ionization constant from this
information.
Ka
H A

1.1 10 1.1 10
-3 -3
HA 0.10
K a 1.2 10 5
44
Bases
Example 18-11: Calculate the concentrations of
various species in 0.15 M acetic acid, CH COOH,
the
3
solution.
It is always a good idea to write down the ionization
reaction and the ionization constant expression.
CH 3COOH H 2 O
H 3O CH 3COO -
Ka
H O CH COO
3

3
-
1.8 10 5
CH 3COOH
45
Bases
Next, combine the basic chemical concepts with
some algebra to solve the problem.

CH 3COOH H 2 O
H 3O CH 3COO -
Initial [] 0.15M
46
Bases
Next we combine the basic chemical concepts with
some algebra to solve the problem

CH 3COOH H 2 O
H 3O CH 3COO -
Initial [] 0.15M
Change - xM xM xM
47
Bases
Next we combine the basic chemical concepts with
some algebra to solve the problem

CH 3COOH H 2 O H 3O CH 3COO -
Initial [] 0.15M
Change - xM xM xM
Equilibrium [] ( 0.15-x)M xM xM
48
Bases
Substitute these algebraic quantities into the
ionization expression.
Ka
H O
3

CH 3COO

CH 3COOH

x x 1.8 10 5
0.15 x
49
Bases
Solve the algebraic equation, using a simplifying assumption that is appropriate for
all weak acid and base ionizations.
x2
1.8 10 5
0.15 x
x 2 0.15 x 1.8 10 5
50
Bases
Solve the algebraic equation, using a simplifying assumption that

is appropriate for all weak acid and base ionizations.
x2 5
1.8 10
0.15 x
x 2 0.15 x 1.8 10 5
Ka 3
If 10 then make this assumption.

x is small enough to ignore compared to [].
x 2 0.151.8 10 5
51
Bases
Complete the algebra and solve for the concentrations of the
species.
x 2 2.7 10 6

x 1.6 10 3 M H 3O CH 3COO
CH 3COOH 0.15 1.6 103 M 0.15M
52
Note that the properly applied simplifying assumption gives
the same result as solving the quadratic equation does.
x x 1.8 10 5
0.15 X
x 2 1.8 10 5 x 2.7 10 6 0
a b c
b b 2 4ac
x
2a
53
Bases
1.8 10 1.8 10 41 2.7 10
5 5 2 6
x
21
x 1.6 10 3 and - 1.6 10-3
54
Bases
Let us now calculate the percent ionization for the
0.15 M acetic acid. From Example 18-11, we know

the concentration of CH3COOH that ionizes in this
solution. The percent ionization of acetic acid is
CH 3COOH ionized
% ionization = 100%
CH 3COOH original
3
1.6 10 M
% ionization 100% 1.1%
0.15M
55
Bases
Example 18-12: Calculate the concentrations
of the species in 0.15 M hydrocyanic acid,

HCN, solution.
Ka= 4.0 x 10-10 for HCN
You do it!
56
H O CN
Bases HCN H O 2 3
-
Initial 0.15 M
Change -xM +xM +xM
Equilibrium 0.15 - x M xM xM
Ka
H CN

x x 4.0 10 10
HCN 0.15 x
x 2 6.0 10 11

x 7.7 10 6 M H CN
HCN 0.15 x M 0.15 M
57
Bases
The percent ionization of 0.15 M HCN solution is
calculated as in the previous example.
% ionization =
HCN ionized
100%
HCN original
7.7 10 6 M
% ionization 100% 0.0051%
0.15M
58
Bases
Lets look at the percent ionization of two weak acids as
a function of their ionization constants. Examples 18-
11 and 18-12 will suffice.
Solution Ka [H+] pH % ionization
0.15 M 1.8 x 10-5 1.6 x 10-3 2.80 1.1
acetic acid
0.15 M 4.0 x 10-10 7.7 x 10-6 5.11 0.0051
HCN
Note that the [H+] in 0.15 M acetic acid is 210 times

greater than for 0.15 M HCN.
59
Bases
All of the calculations and understanding we have at
present can be applied to weak acids and weak

bases!
One example of a weak base ionization is ammonia
ionizing in water.
60
Bases
All of the calculations and understanding we have at
present can be applied to weak acids and weak

bases!
Example 18-13: Calculate the concentrations of the
various species in 0.15 M aqueous ammonia.
NH 3 H 2 O
NH 4 OH -
Initial [] 0.15M
Change - xM xM xM
61
Weak Monoprotic
Acids
NH H O NH OH
and 3 2

4
-
BasesChange
Initial [] 0.15M
- xM xM xM
Kb
NH OH

4
-
x x 1.8 10 5
NH 3 0.15 x
The simplifying assumption is valid.
x 0.15 thus 0.15 - x 0.15
x x x x 1.8 10 5

0.15 x 0.15
x 2 (0.15)1.8 10 5
x 2 2.7 10 6 and x 1.6 10-3 M
NH OH 1.6 10 M

4
- -3
NH 0.15 1.6 10 M 0.15M

3
-3
62
Bases
The percent ionization for weak bases is calculated
exactly as for weak acids.
NH 3 ionized
% ionization 100%
NH 3 original
3
1.6 10 M
100%
0.15M
1.1%
63
Bases
Example 18-14: The pH of an aqueous
ammonia solution is 11.37. Calculate the

molarity (original concentration) of the
aqueous ammonia solution.
You do it!
64
Bases pH = 11.37
From pH + pOH = 14.00, we can derive the pOH.
pOH = 14.00 - pH 14.00 - 11.37 2.63
OH 10 10 2.3 10
- pOH 2.63 3
M
NH 2.3 10 M

4
3
65
Bases
Use the ionization equation and some algebra to get
the equilibrium concentration.

NH 3 H 2 O NH 4 OH -
Initial[] xM
Change - 2.3 10-3 + 2.3 10-3 + 2.3 10-3
-3

Equilibrium[] x - 2.3 10 M + 2.3 10 + 2.3 10
-3 -3
66
Bases
Substitute these values into the ionization constant
expression.
Kb
NH OH

4

1.8 10 5
NH 3
1.8 10 5

2.3 10 2.3 10
3 3
x 2.3 10 3
67
Bases
Examination of the last equation suggests that our
simplifying assumption can be applied.

In other words (x-2.3x10-3) x.
Making this assumption simplifies the calculation.
2.3 10 3 2
1.8 10 5
x
x 0.30 M NH 3
68
Polyprotic Acids
Many weak acids contain two or more acidic hydrogens.
Examples include H3PO4 and H3AsO4.
The calculation of equilibria for polyprotic acids is done in a stepwise fashion.
There is an ionization constant for each step.
Consider arsenic acid, H 3AsO4, which has three ionization constants.
1 Ka1 = 2.5 x 10-4
2 Ka2 = 5.6 x 10-8
3 Ka3 = 3.0 x 10-13
69
Polyprotic Acids
The first ionization step for arsenic acid is:

H 3 AsO 4 H H 2 AsO 4
-
Ka1
H H AsO

2

2.5 10
4 4
H 3AsO4
70
Polyprotic Acids
The second ionization step for arsenic acid is:

H 2 AsO H HAsO 4
1- 2-
4

H HAsO
2
5.6 10 8
H AsO
4
K a2 1-
2 4
71
Polyprotic Acids
The third ionization step for arsenic acid is:

HAsO H AsO 4
2- 3-
4

H AsO
3
3.0 10 13
HAsO
4
K a3 2-
4
72
Polyprotic Acids
Notice that the ionization constants vary in the
following fashion:
K a1 K a2 K a3
This is a general relationship.
For weak polyprotic acids the Ka1 is always > Ka2, etc.
73
Polyprotic Acids
Example 18-15: Calculate the concentration of all
species in 0.100 M arsenic acid, H3AsO4, solution.
1 Write the first ionization step and represent the
concentrations.
Approach this problem exactly as previously done.

H 3 AsO 4 H H 2 AsO 4
0.100 x M xM xM
74
Polyprotic Acids
2 Substitute the algebraic quantities into the
expression for Ka1.
K a1
H H AsO

2

4
2.5 10 4
H 3AsO4
K a1
x x
2.5 10 4
0.10 x
x 2 2.5 10 4 x 2.5 10 5 0
In this case, the simplifying assumption does not apply.
75
Polyprotic Acids
Use the quadratic equation to solve for x, and obtain
both values of x.
x
2.5 10 4
2.5 10
4 2
41 2.5 10 5
21
x 5.110 3 M and x 4.9 10 3 M
H H AsO xM 4.9 10

2

4
3
M
H 3AsO4 0.100 x M 0.095M
76
Polyprotic Acids
4 Next, write the equation for the second step
ionization and represent the concentrations.
H 2 AsO-4 H + + HAsO 2-
4
[ ]from 1st step (4.9 10 M )

-3
algebraically (4.9 10 y ) M
-3
yM yM
77
Polyprotic Acids
5 Substitute the algebraic expressions into the second
step ionization expression.
H O HAsO
2
5.6 10 8
H AsO
3 4
K a2 =
2 4
K =
4.9 10 y y
-3
a2
4.9 10 y
-3
For this step we can apply the assumption.
78
Polyprotic Acids
H O HAsO
5.6 10
2
8
H AsO
3 4
K a2 =
2 4
K =
4.9 10 y y -3
a2
4.9 10 y -3
In this case the assumption can be applied.

y 4.9 10 -3
Thus, 4.9 10 -3 y 4.9 10 -3
K =
4.9 10 y -3
5.6 10 8
a2
4.9 10 -3
y 5.6 10 M H HAsO
8
2nd
2
4
Note that H H
1st

2nd
79
Polyprotic Acids
6 Finally, repeat the entire procedure for the third
ionization step.
HAsO 24
H AsO34-
[ ]' s from 1st and 2 nd ionizations 5.6 10 M 4.9 10
-8 -3
5.6 10-8 M
algebraic representations of [ ] changes 5.6 10 z M
-8
zM zM
80
Polyprotic Acids
7. Substitute the algebraic representations into the

third ionization expression.
H O AsO
3
3.0 10 13
HAsO
3 4
K a3 = 2
4
K a3 =
4.9 10 5.6 10 z z
3 8
5.6 10 z 8
The assumption can be applied, z 5.6 10-8.
81
Polyprotic Acids
4.9 10 z 3.0 10
3
13
5.6 10
8
z 3.4 10 M H AsO
18
3rd
3
4
Use Kw to calculate the [OH-] in the 0.100 M H3AsO4

solution.
H OH 1.0 10
14
OH H 4.9 10
14 14
1.0 10 1.0 10
3
OH 2.0 10 M
12
82
Polyprotic Acids
A comparison of the various species in 0.100 M
H3AsO4 solution follows.
Species Concentration
H3AsO4 0.095 M
H+ 0.0049 M
H2AsO4- 0.0049 M
HAsO42- 5.6 x 10-8 M
AsO43- 3.4 x 10-18 M
OH- 2.0 x 10-12 M
83
Solvolysis
This reaction process is the most difficult concept in this chapter.
Solvolysis is the reaction of a substance with the solvent in which
it is dissolved.
Hydrolysis refers to the reaction of a substance with water or its
ions.
Combination of the anion of a weak acid with H 3O+ ions from
water to form nonionized weak acid molecules.
84
Solvolysis
Hydrolysis refers to the reaction of a
substance with water or its ions.
Hydrolysis is solvolysis in aqueous solutions.
The combination of a weak acids anion with
H3O+ ions, from water, to form nonionized
weak acid molecules is a form of hydrolysis.
A H 3O
-
HA H 2O

recall H 2O + H 2O H 3O OH
85
Solvolysis
The reaction of the anion of a weak monoprotic acid
with water is commonly represented as:
-
A H 2 O HA OH -
+
The removal of H 3O upsets
the water equilibrium
86
Solvolysis
Recall that at 25oC

in neutral solutions:
[H3O+] = 1.0 x 10-7 M = [OH-]
in basic solutions:
[H3O+] < 1.0 x 10-7 M and [OH-] > 1.0 x 10-7 M
in acidic solutions:
[OH-] < 1.0 x 10-7 M and [H3O+] > 1.0 x 10-7 M
87
Solvolysis
Remember from Brnsted-Lowry acid-base theory:
The conjugate base of a strong acid is a very weak base.
The conjugate base of a weak acid is a stronger base.
Hydrochloric acid, a typical strong acid, is essentially
completely ionized in dilute aqueous solutions.
~100%
HCl H 2O H 3O Cl
88
Solvolysis
The conjugate base of HCl, the Cl- ion, is a very weak base.
The chloride ion is such a weak base that it will not react with the hydronium ion.

Cl H 3O No rxn. in dilute aqueous solutions
This fact is true for all strong acids and their anions.
89
Solvolysis
HF, a weak acid, is only slightly ionized in dilute aqueous solutions.
Its conjugate base, the F- ion, is a much stronger base than the Cl -
ion.
The F- ions combine with H3O+ ions to form nonionized HF.
Two competing equilibria are established.
HF + H 2O
H 3O + F-
only slightly
F- + H O +
3 HF + H O 2
nearly completely
90
Solvolysis
Dilute aqueous solutions of salts that
contain no free acid or base come in four
types:
1. Salts of Strong Bases and Strong Acids
2. Salts of Strong Bases and Weak Acids
3. Salts of Weak Bases and Strong Acids
4. Salts of Weak Bases and Weak Acids
91
Salts of Strong Bases and
Strong Acids
(1) Salts made from strong acids and strong soluble
bases form neutral aqueous solutions.

An example is potassium nitrate, KNO3, made from
nitric acid and potassium hydroxide.
KNO3( s ) ~ 100 % in H 2O K + NO3

H 2O H 2O OH - H 3O
The ions that are in solution KOH HNO3
The KOH and HNO3 are present in equal amounts.

There is no reaction to upset H 3O + OH -
Thus the solution is neutral.
92
Weak Acids
(2) Salts made from strong soluble bases and weak acids hydrolyze
to form basic solutions.
Anions of weak acids (strong conjugate bases) react
with water to form hydroxide ions.
An example is sodium hypochlorite, NaClO, made from sodium
hydroxide and hypochlorous acid.
NaClO( s ) ~ 100 % in H 2O Na ClO -

HO + HO
2 2 OH - + H O
3
Notice ions in solution NaOH HClO

Which is the stronger acid or base?
93
Weak Acids
+ - ~100% in H 2O -
Na ClO ( s)
Na ClO
H 2O + H 2O
-
OH + H 3O +
-
ClO H O HClO H O
3 2
We can combine these last two equations into one
single equation that represents the total reaction.
-
ClO H 2O
HClO OH
94
Weak Acids
The equilibrium constant for this reaction, called the
hydrolysis constant, is written as:
HClO OH -
Kb =
ClO -

95
Salts of Strong Bases and Weak
Acids
Algebraic manipulation of the previous expression
give us a very useful form of the expression.
Multiply the expression by one written as [H+]/ [H+].
H+/H+ = 1
HClO OH -
H
Kb =
ClO H
-
Kb =
HClO

H OH
-
H ClO
-
1
96
Salts of Strong Bases and Weak
Acids
Which can be rewritten as:
Kb =
HClO
H OH
-
H ClO
-
1
1
Kb = Kw
Ka for HClO
97
Weak Acids
Which can be used to calculate the hydrolysis
constant for the hypochlorite ion:
1
Kb = Kw
Ka for HClO
Kw 1 10-14
Kb = =
Ka for HClO 3.5 10-8
Kb =
HClO OH
2.9 10 7
ClO
98
Weak Acids
This same method can be applied to the anion of
any weak monoprotic acid.

A H 2 O HA OH -
HA OH
KW
Kb =
A
K a for HA
99
Weak Acids
Example 18-16: Calculate the hydrolysis constants
for the following anions of weak acids.
1. The fluoride ion, F-, the anion of hydrofluoric acid,
HF. For HF, Ka=7.2 x 10-4.
F H 2 O
HF OH
HF OH Kw
Kb
F

Ka for HF
. 1014
10 11
Kb 14
. 10
7.2 104
100
Weak Acids
The cyanide ion, CN-, the anion of hydrocyanic acid, HCN.
For HCN, Ka = 4.0 x 10-10.
You do it!
HCN + OH -
CN H 2 O
HCN OH Kw

Kb
CN
K a for HCN
14
1.0 10 5
Kb 10
2.5 10
4.0 10
101
Weak Acids
Example 18-17: Calculate [OH-], pH and percent
hydrolysis for the hypochlorite ion in 0.10 M sodium
hypochlorite, NaClO, solution. Clorox, Purex,
etc., are 5% sodium hypochlorite solutions.
in H 2O Na ClO
NaClO(s) ~ 100%
0.10 M 0.10 M 0.10 M
102
Weak Acids
Set up the equation for the hydrolysis and the
algebraic representations of the equilibrium
concentrations.
-
ClO + H 2 O HClO + OH -
Initial: 0.10 M 0M 0M
Change: - xM + xM + xM
At equil: 0.10 - x M xM xM
103
Weak Acids
Substitute the algebraic expressions into the
hydrolysis constant expression.
HClO OH
2.9 10 7

Kb
ClO
Kb
x x
2.9 10 7
010
. x
104
Weak Acids
Substitute the algebraic expressions into the
hydrolysis constant expression.
The simplifying assumption can be made in this case.
x 0.10 and 0.10 - x 0.10
The equation reduces to x 2 2.9 10 8

Which becomes x 1.7 10 4 M ClO OH
From the [OH - ] we get the pOH 3.77
From pH pOH 14.00 we get the pH 10.23.
105
Weak Acids
The percent hydrolysis for the hypochlorite ion may
be represented as:
ClO -
hydrolyzed
100%
% hydrolysis =
ClO -
original
1.7 10 M -4
% hydrolysis = 100% 0.17%
0.10 M
106
Weak Acids
If a similar calculation is performed for 0.10 M NaF
solution and the results from 0.10 M sodium fluoride
and 0.10 M sodium hypochlorite compared, the
following table can be constructed.
%
Solution Ka Kb [OH-] (M) pH hydrolysis
NaF 7.2 x 10-4 1.4 x 10-11 1.2 x 10-6 8.08 0.0012
NaClO 3.5 x 10-8 2.9 x 10-7 1.7 x 10-4 10.23 0.17
107
Salts of Weak Bases and
Strong Acids
(3) Salts made from weak bases and strong acids
form acidic aqueous solutions.
An example is ammonium bromide, NH4Br, made
from ammonia and hydrobromic acid.

NH 4 Br s
H 2 O ~100%
NH 4 Br -

H 2O H 2O
OH - H 3O
Ions in solution are NH 4OH HBr
Which is the stronger acid or base?
108
Strong Acids
The relatively strong acid, NH ,
4
reacts with the OH - ion removing

it from solution leaving excess H 3O
NH H O
NH OH -
4 3 2
generates excess H 3O
The reaction may be more simply represented as:

NH H 2 O
NH 3 H 3O
4
109
Strong
Or even moreAcids
simply as:

NH

NH 3 H
4
The hydrolysis constant expression for this process
is:
NH 3 H 3O or K NH H

NH NH
3
Ka a
4 4
110
Strong Acids
Multiplication of the hydrolysis constant expression
by [OH-]/ [OH-] gives:
NH 3 H 3O
OH -

Ka
NH
4 OH -

NH

H O OH -
NH OH
3 3
Ka -
4 1
111
Strong Acids
Which we recognize as:
1 Kw Kw
Ka
K b NH 3 1 K b NH 3
14
. 10
10 10
Ka 5 5.6 10
18. 10
112
Strong Acids
In its simplest form for this hydrolysis:

NH 4 NH H
3
NH 3 H
5.6 10 10
Ka

NH 4
113
Strong Acids
Example 18-18: Calculate [H+], pH, and percent
hydrolysis for the ammonium ion in 0.10 M
ammonium bromide, NH4Br, solution.
1. Write down the hydrolysis reaction and set up the
table as we have done before:
NH 4+ H 2O
NH 3 H
Initial[]: 0.10 M + xM + xM
Change: - xM + xM + xM
Equilibrium[]: 0.10 x M xM xM
114
Strong Acids
2. Substitute the algebraic expressions into the
hydrolysis constant.
NH 3 H
5.6 10 10
Ka
NH
4
Ka
x x = 5.6 10 -10
0.10 x
The assumption is applicable.
x 0.10 thus 0.10 - x 0.10
115
Strong Acids
3. Complete the algebra and determine the
concentrations and pH.
x x 5.6 10 10
0.10 x
x 2 5.6 10 11
x = 7.5 10 -6 M
NH H 7.5 10
3
-6
M
pH 5.12
116
Strong Acids
4. The percent hydrolysis of the ammonium ion in
0.10 M NH4Br solution is:
% hydrolysis =
NH 4+ hydrolized
100%
+
NH 4
original
7.5 10-6 M
% hydrolysis = 100%
010
. M
% hydrolysis = 0.0075%
117
Weak
Acids
(4) Salts made from weak acids and weak bases
can form neutral, acidic or basic aqueous
solutions.
The pH of the solution depends on the relative values of
the ionization constant of the weak acids and bases.
1. Salts of weak bases and weak acids for which
parent Kbase =Kacid make neutral solutions.
An example is ammonium acetate, NH4CH3COO,
made from aqueous ammonia, NH3,and acetic
acid, CH3COOH.
Ka for acetic acid = Kb for ammonia = 1.8 x 10-5.
118
Weak Acids
The ammonium ion hydrolyzes to produce H+ ions.
Its hydrolysis constant is:
+
NH 4
NH 3 H
NH 3 H
5.6 10 10
Ka
+
NH 4
119
Weak Acids
The acetate ion hydrolyzes to produce OH- ions. Its
hydrolysis constant is:

CH 3COO H 2O CH 3COOH OH
CH 3COOH OH
5.6 10 10
Kb
CH COO
3

120
Weak Acids
Because the hydrolysis constants for both ions are
equal, their aqueous solutions are neutral.
Equal numbers of H+ and OH- ions are produced.
NH 4 CH 3COO H 2O ~100%
NH 4 CH 3COO
HO HO
2 2 OH - H O 3
Ions in solution are NH 4OH CH 3COOH

A weak acid and base are formed in solution!
121
Weak Acids
2. Salts of weak bases and weak acids for
which parent Kbase > Kacid make basic
solutions.
An example is ammonium hypochlorite,
NH4ClO, made from aqueous ammonia,
NH3,and hypochlorous acid, HClO.
Kb for NH3 = 1.8 x 10-5 > Ka for HClO = 3.5x10-8
122
Weak Acids
The ammonium ion hydrolyzes to produce H+ ions.

NH NH 3 H
4
NH 3 H
5.6 10 10

Ka
NH
4
123
Weak Acids
The hypochlorite ion hydrolyzes to produce OH - ions.

ClO H 2O HClO OH
HClO OH
2.9 10 7
K
Because
ClO
b the Kb for ClO- ions-is three orders of
magnitude larger than the Ka for NH4+ ions, OH- ions
are produced in excess making the solution basic.
124
Weak Acids
3. Salts of weak bases and weak acids for which
parent Kbase < Kacid make acidic solutions.
An example is trimethylammonium fluoride,
(CH3)3NHF, made from trimethylamine,
(CH3)3N,and hydrofluoric acid acid, HF.
Kb for (CH3)3N = 7.4 x 10-5 < Ka for HF = 7.2 x 10-4
125
Weak Acids
Both the cation, (CH3)3NH+, and the anion, F-,
hydrolyze.
CH 3 3 NH CH 3 3 NH F
H 2 O~100%
F
126
Weak Acids
The trimethylammonium ion hydrolyzes to produce
H+ ions. Its hydrolysis constant is:
+
(CH 3 ) 3 NH (CH 3 ) 3 N H
Ka
33
( CH ) N
H
Kw
(CH ) NH K
3 3
+
b for ( CH 3 ) 3 N
14
. 10
10 10
Ka 5 14
. 10
7.4 10
127
Weak Acids
The fluoride ion hydrolyzes to produce OH- ions. Its
hydrolysis constant is:

F H 2O HF OH
HF OH
Kw
Kb
F
-
Ka for HF
Because the Ka for (CH3)3NH+ ions is one order of
14
10
magnitude larger 10the Kb for F- ions,H11+ ions are
. than
K 4
produced bin excess making
. 10
14
the solution acidic.
7.2 10
128
Weak
Acids
Summary of the major points of
hydrolysis up to now.
1 The reactions of anions of weak monoprotic
acids (from a salt) with water to form free
molecular acids and OH-.
-
A + H 2O HA + OH -
Kw
Kb HA = weak
Ka HA acid
129
Weak Acids
2. The reactions of cations of weak monoprotic bes
(from a salt) with water to form free molecular bes
and H3O+.
+
BH + H 2 O B + H 3O +
Kw
Ka B = weak base
K b B
130
Weak Acids
Aqueous solutions of salts of strong acids and
strong bases are neutral.
Aqueous solutions of salts of strong bases
and weak acids are basic.
Aqueous solutions of salts of weak bases and
strong acids are acidic.
Aqueous solutions of salts of weak bases and
weak acids can be neutral, basic or acidic.
The values of Ka and Kb determine the pH.
131
Hydrolysis of Small Highly-
Charged Cations
Cations of insoluble bases (metal hydroxides) become
hydrated in solution.
An example is a solution of Be(NO3)2.
Be2+ ions are thought to be tetrahydrated and sp3 hybridized.
1s 2s 2 2p
Be 2
Be 2+
aq

Be(OH 2 )
4

1s 2s 2p
form sp 3
hybrids
Be(OH 2 ) 4 2

Be xx xx xx
xx
4
e- pairs on coordinated water molecules
132
Charged Cations
In condensed form it is represented as:
H 2O Be OH OH 2 3 H 3O

Be(OH 2 )4 2
or, even more simply as:

Be 2+
H 2 O Be(OH) H
133
Charged Cations
The hydrolysis constant expression for [Be(OH2)4]2+
and its value are:
Ka
Be(OH ) (OH) H O
2 3
+
3
10

. 10 5
Be(OH )
2
2 4
or, more simply
Ka
Be(OH) H
+
10

. 10 5
Be 2+
134
Charged Cations
Example 18-19: Calculate the pH and percent
hydrolysis in 0.10 M aqueous Be(NO3)2 solution.
1. The equation for the hydrolysis reaction and
representations of concentrations of various
species are:
2
Be H 2 O Be(OH) H
0.10 x M xM xM
135
Charged Cations
2. Algebraic substitution of the expressions into the
hydrolysis constant:
x x 1.0 10 5
0.10 x
The simplifying assumption applies.
x 0.10 and 0.10 - x 0.10
x x 1.0 10 5
0.10
x 2 1.0 10 6
x 1.0 10 3 M
H Be
2
hydrolyzed 1. 0 10 3
M
pH 3.00
136
Charged Cations
3 Calculate the percent hydrolysis of Be2+.
% hydrolyzed =
Be 2+
hydrolyzed
100%
Be 2+
original
-3
1.0 10
% hydrolyzed = 100% 10%
.
0.10
137
Charged Cations
This table is a comparison of 0.10 M Be(NO3 )2
solution and 0.10 M CH3COOH solution.
% hydrolysis or
Solution [H3O+] pH % ionization
0.10 M Be(NO3)2 1.0 x 10-3 M 3.00 1.0%
0.10 M CH3COOH 1.3 x 10-3 M 2.89 1.3%
Notice that the Be solution is almost as acidic as the acetic

acid solution.
138
Synthesis Question
Rain water is slightly acidic because it
absorbs carbon dioxide from the atmosphere
as it falls from the clouds. (Acid rain is even
more acidic because it absorbs acidic
anhydride pollutants like NO2 and SO3 as it
falls to earth.) If the pH of a stream is 6.5
and all of the acidity comes from CO2, how
many CO2 molecules did a drop of rain
having a diameter of 6.0 mm absorb in its fall
to earth?
139
Synthesis Question

pH 6.5 H 10 6.5 3.2 10-7 M
CO 2 H 2 O H 2 CO 3

H CO H HCO -
2 3 3
Ka
H HCO

4.2 10
3 7
H 2CO3
Ka
3.2 10 3.2 10
7 7
4.2 10 7
H 2CO3
H 2CO3 2.4 10 7
M 2.4 10 7 mol
L
140
Synthesis Question
volume of water droplet 4 3 r 3 4 3 0.3 cm
3
0.11 cm 3 1L 1000cm3 1.1 104 L

number of CO2 molecules 1.1 104 L 2.4 107 mol L
11 6.022 10 23
molecules
2.6 10 mol
mol
1.6 1013 CO2 molecules
141
Group Question
A common food preservative in citrus flavored

drinks is sodium benzoate, the sodium salt of
benzoic acid. How does this chemical
compound behave in solution so that it
preserves the flavor of citrus drinks?
142
End of Chapter 18
Weak aqueous acid-base mixtures are called buffers.
They are the subject of Chapter 19.
143

5 (II) - Ionic Equilibria-Acid Bes

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5 (II) - Ionic Equilibria-Acid Bes

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Chapter 18

Ionic Equilibria: Acids and Bases

1. A Review of Strong Electrolytes

8. Salts of Strong Bases and Weak Acids

0.020 M 0.020M 2 0.020M

Because the activity of pure water is 1, the

The [H 3O ] from K w is 2.0 10 -13 M .

and so forth for other quantities.

pOH log5.0 10 12.30

[H3O+] [OH-] pH pOH

The equilibrium constant for this ionization is

magnitude greater than the ion concentrations.

acid equilibria that uses the previous definition.

acid ionization expression are written as:

increasing acid strength for these weak acids is:

of the weak acid HCN and the expression for its

some algebra to solve the problem.

some algebra to solve the problem

some algebra to solve the problem

is appropriate for all weak acid and base ionizations.

0.15 M acetic acid. From Example 18-11, we know

of the species in 0.15 M hydrocyanic acid,

calculated as in the previous example.

Note that the [H+] in 0.15 M acetic acid is 210 times

present can be applied to weak acids and weak

present can be applied to weak acids and weak

NH 0.15 1.6 10 M 0.15M

exactly as for weak acids.

ammonia solution is 11.37. Calculate the

the equilibrium concentration.

simplifying assumption can be applied.

[ ]from 1st step (4.9 10 M )

For this step we can apply the assumption.

In this case the assumption can be applied.

7. Substitute the algebraic representations into the

The assumption can be applied, z 5.6 10-8.

Use Kw to calculate the [OH-] in the 0.100 M H3AsO4

Recall that at 25oC

bases form neutral aqueous solutions.

KNO3( s ) ~ 100 % in H 2O K + NO3

NaClO( s ) ~ 100 % in H 2O Na ClO -

Notice ions in solution NaOH HClO

NaClO 3.5 x 10-8 2.9 x 10-7 1.7 x 10-4 10.23 0.17

reacts with the OH - ion removing

Ions in solution are NH 4OH CH 3COOH

or, even more simply as:

0.10 M CH3COOH 1.3 x 10-3 M 2.89 1.3%

Notice that the Be solution is almost as acidic as the acetic

0.11 cm 3 1L 1000cm3 1.1 104 L

A common food preservative in citrus flavored

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