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Lecture Unit 5
BASIC CHEMICAL AND IONIC EQUILIBRIA
1
Unit Goals
2
Basic Concepts
3
Basic Concepts
4
Basic Concepts
Graphically, this is a representation of the
rates for the forward and reverse reactions
for this general reaction.
cC +dD
a Ag + b Bg g g
5
Basic Concepts
6
The Equilibrium Constant
7
The Equilibrium Constant
Kc
C D
A B
9
The Equilibrium Constant
Kc
C D
c d
products
A B
a b reactants
PCl5 PCl3 Cl2
Kc
PCl3 Cl2
PCl5 12
The Equilibrium Constant
H 2 + I 2 2 HI
You do it!
13
The Equilibrium Constant
H 2 + I 2 2 HI
Kc
HI
2
H 2 I 2
14
The Equilibrium Constant
4 NH3 + 5 O 2 4 NO + 6 H 2O
You do it!
15
The Equilibrium Constant
4 NH3 + 5 O 2 4 NO + 6 H 2O
Kc =
NO H 2O
4 6
NH3 O 2
4 5
16
The Equilibrium Constant
17
The Equilibrium Constant
18
The Equilibrium Constant
Kc
PCl3 Cl2
PCl5
Kc
0.1720.086
0.028
K c 0.53
19
The Equilibrium Constant
20
The Equilibrium Constant
PCl5g PCl3g Cl2g
Initial 1.00 M 0 0
21
The Equilibrium Constant
PCl5g PCl3g Cl2g
Initial 1.00 M 0 0
Change - 0.60 M + 0.60 M + 0.60 M
22
The Equilibrium Constant
PCl5g PCl3g Cl2g
Initial 1.00 M 0 0
Change - 0.60 M + 0.60 M + 0.60 M
Equilibriu m 0.40 M 0.60 M 0.60 M
23
The Equilibrium Constant
PCl5g PCl3g Cl2g
Initial 1.00 M 0 0
Change - 0.60 M + 0.60 M + 0.60 M
Equilibriu m 0.40 M 0.60 M 0.60 M
K '
0.60 0.60
0.90 at another T
c
0.40 24
The Equilibrium Constant
25
The Equilibrium Constant
N 2(g) + 3 H 2(g) 2 NH3(g)
Initial 0.80 M 0.90 M 0
Change - 0.10 M - 0.30 M + 0.20 M
Equilibriu m 0.70 M 0.60 M 0.20 M
Kc
NH3
2
0.20
2
0.26
N 2 H 2 0.700.60
3 3
26
Variation of Kc with the
Form of the Balanced Equation
The value of Kc depends upon how the balanced
equation is written.
From example 17-2 we have this reaction:
PCl5 PCl3 Cl2
This reaction has a Kc=[PCl3][Cl2]/[PCl5]=0.53
27
Variation of Kc with the
Form of the Balanced Equation
Example 17-5: Calculate the equilibrium constant
for the reverse reaction by two methods, i.e, the
equilibrium constant for this reaction.
PCl3 Cl2 PCl5
Equil. []‟s 0.172 M 0.086 M 0.028 M
The concentrations are from Example 17-2.
28
Variation of Kc with the
Form of the Balanced Equation
Kc
' PCl5
0.028
1.9
PCl3 Cl2 0.1720.086
Kc 1 ' or '
Kc 1 K 10.53 1.9
Kc c
Large equilibrium constants indicate that most of
the reactants are converted to products.
Small equilibrium constants indicate that only
small amounts of products are formed.
29
The Reaction Quotient
The mass action expression or reaction quotient
has the symbol Q.
Q has the same form as Kc
The major difference between Q and Kc is that
the concentrations used in Q are not
necessarily equilibrium values.
For this general reaction :
aA + bB cC + dD
Q
C D
c d
A B
a b
30
The Reaction Quotient
31
The Reaction Quotient
When :
Q = K c The system is at equilibriu m.
Q K c The reaction occurs to the left to a greater extent.
Q K c The reaction occurs to the right to a greater extent.
To help understand this think of Q and K c as fractions.
32
The Reaction Quotient
Example 17-6: The equilibrium constant for the
following reaction is 49 at 450oC. If 0.22 mole of
I2, 0.22 mole of H2, and 0.66 mole of HI were put
into an evacuated 1.00-liter container, would the
system be at equilibrium? If not, what must
occur to establish equilibrium?
33
The Reaction Quotient
The concentrat ions given in the problem
are not necessaril y equilibriu m []' s.
We can calculate Q.
2 HI
H 2(g) I 2(g) (g)
Q=
HI
2
0.66
2
9.0
H 2 I 2 0.220.22
Q 9.0 but K c 49
Q < Kc
34
Uses of the Equilibrium Constant, Kc
35
Uses of the Equilibrium Constant, Kc
SO 2(g) NO2(g)
SO3(g) NO(g)
Initial 0.500 M 0.500 M 0 0
36
Uses of the Equilibrium Constant, Kc
SO 2(g) NO2(g)
SO3(g) NO(g)
Initial 0.500 M 0.500 M 0 0
Change - xM - xM +xM +xM
37
Uses of the Equilibrium Constant, Kc
SO 2(g) NO2(g)
SO 3(g) NO(g)
Initial 0.500 M 0.500 M 0 0
Change - xM - xM +xM +xM
Equilibriu m 0.500 x M 0.500 x M xM xM
38
Uses of the Equilibrium Constant, Kc
SO 2(g) NO2(g)
SO 3(g) NO(g)
Initial 0.500 M 0.500 M 0 0
Change - xM - xM +xM +xM
Equilibriu m 0.500 x M 0.500 x M xM xM
Kc
SO3 NO 3.00 x x
SO 2 NO2 0.500 x 0.500 x
This equation is a perfect square .
We can take the of both sidesof the equation.
39
Uses of the Equilibrium Constant, Kc
SO 2(g) NO2(g)
SO 3(g) NO(g)
Initial 0.500 M 0.500 M 0 0
Change - xM - xM +xM +xM
Equilibriu m 0.500 x M 0.500 x M xM xM
Kc
SO 3 NO
3.00
x x
SO 2 NO2 0.500 x 0.500 x
This equation is a perfect square.
We can take the of both sides.
x
1.73 =
0.500 x
0.865 - 1.73 x x; 0.865 2.73 x; x 0.865
2.73
x 0.316M SO 3 NO
0.500 x M 0.184M SO 2 NO2
40
Uses of the Equilibrium Constant, Kc
Initial 0 0 1.00M
Change + xM + xM - 2x M
Equilibriu m xM xM 1.00 - 2 x M
Kc =
HI
2
= 49 =
1.00 - 2 x
2
H 2 I 2 x x
K = 7.0 =
1.00 - 2 x
c
x
7.0 x 1.00 2 x; 9 x 1.00; x 0.11 M
H 2 I 2 xM 0.11 M
HI 1.00 2 x M 0.78 M
42
Le Chatelier’s Principle
44
Le Chatelier’s Principle
PV nRT
n
P RT
V
n
Because has the units mol/L,
V
P = []RT
Thus at constant T, the partial pressure of a gas
is directly proportion al to its concentrat ion.
45
Le Chatelier’s Principle
2 HI
H2 I2 g
Kc
HI
49
2
H 2 I 2
46
Le Chatelier’s Principle
Kc
HI
2
49
H 2 I 2
If some H 2 is added, Q < K c .
This favors the forward reaction.
Equilbrium will shift to the right or product side. 47
Le Chatelier’s Principle
Kc
HI
2
49
H 2 I 2
If we remove some H 2 , Q > K c
This favors the reverse reaction.
Equilbrium will shift to the left, or reactant side. 48
Le Chatelier’s Principle
2 Changes in Volume
• (and pressure for reactions involving gases)
Predict what will happen if the volume of this system at
2 NO2g N 2O 4g
Kc =
N 2O 4
NO2 2
49
Le Chatelier’s Principle
N O
2 NO2g 2 4 g
Kc =
N 2O 4
NO2 2
If the volume is decreased, which increases the pressure, Q < K c .
This favors product formation or the forward reaction.
The forward reaction produces fewer moles of gas.
50
Le Chatelier’s Principle
N O
2 NO2g 2 4 g
Kc =
N 2O 4
NO2 2
51
Le Chatelier’s Principle
2 SO + 198 kJ
2 SO 2g + O 2g 3 g
52
Le Chatelier’s Principle
Introduction of a Catalyst
Catalysts decrease the activation energy of both the forward and
reverse reaction equally.
53
Le Chatelier’s Principle
54
Partial Pressures and the Equilibrium
Constant
For gas phase reactions the equilibrium
constants can be expressed in partial pressures
rather than concentrations.
For gases, the pressure is proportional to the
concentration.
We can see this by looking at the ideal gas law.
PV = nRT
P = nRT/V
n/V = M
P= MRT and M = P/RT
55
Partial Pressures and the Equilibrium
Constant
Consider this system at equilibrium at 5000C.
4 HCl + O
2 Cl2g + 2 H 2Og g 2 g
HCl O 2
4
PHCl PO
4
Kc and K p
PCl PH O
2
Cl2 H 2O
2 2 2
2
2
2
56
Partial Pressures and the Equilibrium
Constant
Kc
PHCl 4 PO2
PHCl PO 4
1 5
P P
RT RT 2 RT
P 2 P 2 2 2 1 4
Cl2 H 2O
RT RT Cl 2 H 2O RT
Kc K so for this
1
p RT reaction
-1 1
K c = K p (RT) or K p = K c (RT)
L atm
Must use R 0.0821
mol K
57
Relationship Between Kp and Kc
K p K c RT or K c K p RT
n n
58
Relationship Between Kp and Kc
2 NOBrg
2 NOg + Br2g
59
Relationship Between Kp and Kc
2 NOBrg
2 NOg + Br2g
Initial [] x atm 0 0
Change - 0.34 x atm + 0.34 x atm + 0.17 x atm
Equilibriu m x - 0.34 x atm 0.34 xatm 0.17 x atm
60
Relationship Between Kp and Kc
61
Relationship Between Kp and Kc
PNOBr 2
0.14 2
62
Relationship Between Kp and Kc
K p = Kc RT or Kc = K p RT
n n
n = 1
Kc 9.3 10 3
0.08212981
38
. 10 4
63
Relationship Between Kp and Kc
64
Relationship Between Kp and Kc
H 2 g 2 HI
I 2 g g
Initial 0.33M 0.33M 0
Change -xM -xM + 2x M
Equilibriu m 0.33 - x M 0.33 - x M 2x M
Kc =
HI
2
49
2x
2
7.0
2x
H 2 I 2 0.33 - x 2
0.33 - x
9 x = 2.3; x = 0.256 M
[H 2 ] [I 2 ] (0.33 x) M 0.074 M
HI 2 x M 0.51M
? mol I 2 3.0 L 0.074 mol L 0.21 mol 65
Relationship Between Kp and Kc
66
Relationship Between Kp and Kc
67
Relationship Between Kp and Kc
68
Relationship Between Kp and Kc
69
Heterogeneous Equlibria
Heterogeneous equilibria have more than one
phase present.
For example, a gas and a solid or a liquid and a gas.
CaCO3s
CaOs CO2g at 500 C o
K c = [CO 2 ] K p = PCO 2
70
Heterogeneous Equlibria
For this reaction :
H SO
SO 2aq H 2 O o
(at 25 C)
2 3aq
H 2 O is the solvent.
What are the forms of K c and K p?
You do it!
Kc =
H 2SO3
K p is undefined
SO 2
71
Heterogeneous Equlibria
Kc = Ca 2
F
2
K p is undefined
72
Heterogeneous Equlibria
P
4
Kc =
H2
4
Kp
H2
H 2 O P
4 4
H 2O
73
Evaluation of Equilibrium Constants at
Different Temperatures
From the value of Ho and K at one
temperature, T1, we can use the van‟t Hoff
equation to estimate the value of K at
another temperature, T2.
K T2 H (T2 T1 )
o
ln
K T1 R T2 T1
or
K T2 H o
1 1
ln
K T1 R T1 T2 74
Evaluation of Equilibrium Constants at
Different Temperatures
Example 17-19: For the reaction in example
17-18, Ho = 114 kJ/mol and Kp = 4.3 x 10-13
at 25oC. Estimate Kp at 250oC.
2 NO2(g) 2 NO(g) + O2(g)
75
Evaluation of Equilibrium Constants
at Different Temperatures
Let T1 298 K and T2 523 K
apply the van' t Hoff equation
76
Evaluation of Equilibrium Constants
at Different Temperatures
Let T1 298 K and T2 523 K
apply the van' t Hoff equation
K T2 (1.14 10 mol )523 298
5 J
ln
K T1 8.314 J mol K 523 K 298 K
K T2
ln 19.795
K T1
77
Evaluation of Equilibrium Constants at
Different Temperatures
Take the antilog of both sides of equation.
K T2
e19.80 4.0 108
K T1
Solve for K T2 & substitute the known valu e of K T1
K T2 4.0 108 K T1 4.0 108 4.3 10-13
4
K T2 1.7 10 @ 250 C vs K T1 4.3 10
o -13 o
@ 25 C
The reaction is more product favored at the higher T.
78
Ionic Equilibria Basic Concept
This 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 unit we will see that it is often less than 10%!
Strong electrolytes ionize or dissociate
completely.
Strong electrolytes approach 100% dissociation in
aqueous solutions.
79
Ionic Equilibria Basic Concept
There are three classes of strong electrolytes.
1 Strong Water Soluble Acids
Remember the list of strong acids from Chapter 4.
100%
HNO3( ) H 2O ( ) H 3O (aq) NO 3(aq)
or
100%
HNO3( ) H (aq) NO 3(aq)
80
Ionic Equilibria Basic Concept
10 0%
HNO 3( ) H 2O ( ) H 3O (aq) NO 3(aq)
or
10 0%
HNO 3( ) H (aq) NO 3(aq)
81
Ionic Equilibria Basic Concept
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)
82
Ionic Equilibria Basic Concept
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 ) 2s Ca (aq) 2 NO 3(aq)
83
Ionic Equilibria Basic Concept
84
Ionic Equilibria Basic Concept
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)
85
The Autoionization of Water
86
The Autoionization of Water
equilibrium constant for this reaction is:
Kc H 3O +
OH
87
The Autoionization of Water
Kc H 3O OH
+
1.0 x 10 1.0 x 10
-7 -7
14
1.0 x10
88
The Autoionization of Water
K w H 3O +
OH
14
1.0 x10
89
The Autoionization of Water
Example 18-3: Calculate the concentrations of
H3O+ and OH- in 0.050 M HCl.
HCl + H 2 O H 3O + Cl
0.050M 0.050M 0.050M
Thus the H 3O + 0.050M .
The H 3O + and K w will allow us to calculate [OH - ].
90
The Autoionization of Water
91
The Autoionization of Water
92
The Autoionization of Water
The pH of an aqueous solution is defined as:
+
pH = -log H 3O
94
The pH and pOH scales
pOH = -log OH -
pAg = -logAg +
95
The pH and pOH scales
pH = -log H 3O +
pH log 3.0 10 2
pH 1.52
96
The pH and pOH scales
log H 3O log OH 14.00
98
The pH and pOH scales
- log H 3O log OH
14.00
Which can be rearranged to this form:
pH pOH 14.00
99
The pH and pOH scales
pH pOH 14.00
100
The pH and pOH scales
pH 1.70
102
The pH and pOH scales
103
The pH and pOH scales
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.
104
Ionization Constants for Weak
Monoprotic Acids and Bases
Let‟s look at the dissolution of acetic acid, a weak
acid, in water as an example.
The equation for the ionization of acetic acid is:
CH3COOH H 2O H3O CH3COO-
Kc
H O CH COO
3
3
CH3COOHH 2O
105
Ionization Constants for Weak
Monoprotic Acids and 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:
H2O 55.5M
106
Ionization Constants for Weak
Monoprotic Acids and 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
CH3COOH
K
H O CH COO
3
3
CH3COOH
107
Ionization Constants for Weak
Monoprotic Acids and 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
CH3COOH
for acetic acid
108
Ionization Constants for Weak
Monoprotic Acids and Bases
In simplified form the dissociation equation and
acid ionization expression are written as:
CH3COOH H CH3COO-
Ka
H CH COO
3
1.8 10 5
CH3COOH
109
Ionization Constants for Weak
Monoprotic Acids and 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
110
Ionization Constants for Weak
Monoprotic Acids and Bases
From the above table we see that the order of
increasing acid strength for these weak acids is:
HF > HNO2 > CH3COOH > HClO > HCN
The order of increasing base strength of the anions
(conjugate bases) of these acids is:
- - - - -
F < NO < CH3COO < ClO < CN
2
111
Ionization Constants for Weak
Monoprotic Acids and 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
112
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
113
Ionization Constants for Weak
Monoprotic Acids and Bases
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
114
Ionization Constants for Weak
Monoprotic Acids and Bases
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
K a 3.3 10 4
115
Ionization Constants for Weak
Monoprotic Acids and Bases
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
116
Ionization Constants for Weak
Monoprotic Acids and Bases
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
117
Ionization Constants for Weak
Monoprotic Acids and Bases
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
118
Ionization Constants for Weak
Monoprotic Acids and Bases
Example 18-11: Calculate the concentrations of the
various species in 0.15 M acetic acid, CH3COOH,
solution.
It is always a good idea to write down the ionization
reaction and the ionization constant expression.
CH3COOH H 2 O
H 3O CH 3COO-
Ka
H O CH COO
3
3
-
1.8 10 5
CH3COOH
119
Ionization Constants for Weak
Monoprotic Acids and Bases
Next, combine the basic chemical concepts with
some algebra to solve the problem.
CH3COOH H 2O
H 3O CH3COO-
Initial [] 0.15M
120
Ionization Constants for Weak
Monoprotic Acids and Bases
Next we combine the basic chemical concepts with
some algebra to solve the problem
CH3COOH H 2O
H 3O CH3COO-
Initial [] 0.15M
Change - xM xM xM
121
Ionization Constants for Weak
Monoprotic Acids and Bases
Next we combine the basic chemical concepts with
some algebra to solve the problem
CH3COOH H 2O H 3O CH3COO-
Initial [] 0.15M
Change - xM xM xM
Equilibriu m [] ( 0.15-x)M xM xM
122
Ionization Constants for Weak
Monoprotic Acids and Bases
Substitute these algebraic quantities into the
ionization expression.
Ka
H 3 O
CH
3 COO
CH 3COOH
x x 1.8 10 5
0.15 x
123
Ionization Constants for Weak
Monoprotic Acids and Bases
Solve the algebraic equation, using a simplifying assumption that
is appropriate for all weak acid and base ionizations.
2
x
1.8 10 5
0.15 x
x 2 0.15 x 1.8 10 5
124
Ionization Constants for Weak
Monoprotic Acids and 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
Ka
10 3 then make this assumption .
If
x is small enough to ignore compared to [].
x 0.151.8 10
2 5
125
Ionization Constants for Weak
Monoprotic Acids and 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
CH3COOH 0.15 1.6 103 M 0.15M
126
Ionization Constants for Weak
Monoprotic Acids and Bases
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
5 6
x 1.8 10 x 2.7 10
2
0
a b c
b b 2 4ac
x
2a
127
Ionization Constants for Weak
Monoprotic Acids and Bases
x
1.8 10 5
1.8 10
5 2
41 2.7 10 6
21
x 1.6 10 3 and - 1.6 10-3
128
Ionization Constants for Weak
Monoprotic Acids and 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
CH3COOHionized
% ionization = 100%
CH3COOHoriginal
3
1.6 10 M
% ionization 100% 1.1%
0.15M
129
Ionization Constants for Weak
Monoprotic Acids and 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!
130
Ionization Constants for Weak
Monoprotic Acids and Bases
H O CN -
HCN H 2 O 3
Initial 0.15 M
Change -xM +xM +xM
Equilibriu m 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
131
Ionization Constants for Weak
Monoprotic Acids and Bases
The percent ionization of 0.15 M HCN solution is
calculated as in the previous example.
% ionization =
HCN ionized
100%
HCN original
6
7.7 10 M
% ionization 100% 0.0051%
0.15M
132
Ionization Constants for Weak
Monoprotic Acids and Bases
Let‟s 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
133
Ionization Constants for Weak
Monoprotic Acids and 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.
134
Ionization Constants for Weak
Monoprotic Acids and 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.
NH3 H 2 O
NH4 OH-
Initial [] 0.15M
Change - xM xM xM
Equilibriu m [] ( 0.15-x)M xM xM
135
Ionization Constants for Weak
Monoprotic Acids and
NH H O
Bases
NH OH -
3 2 4
Initial [] 0.15M
Change - xM xM xM
Equilibriu m [] ( 0.15-x)M xM xM
Kb
NH OH
4
-
x x 1.8 10 5
NH3 0.15 x
The simplifyin g assumption is valid.
x 0.15 thus 0.15 - x 0.15
x x x x 1.8 105
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
136
Ionization Constants for Weak
Monoprotic Acids and Bases
The percent ionization for weak bases is calculated
exactly as for weak acids.
NH3 ionized
% ionization 100%
NH3 original
3
1.6 10 M
100%
0.15M
1.1%
137
Ionization Constants for Weak
Monoprotic Acids and 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!
138
Ionization Constants for Weak
Monoprotic Acids and 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
139
Ionization Constants for Weak
Monoprotic Acids and Bases
Use the ionization equation and some algebra to get
the equilibrium concentration.
NH3 H 2O NH4 OH -
Initial[] xM
Change - 2.3 10-3 + 2.3 10-3 + 2.3 10-3
Equilibriu m[] x - 2.3 10-3 M + 2.3 10-3 + 2.3 10-3
140
Ionization Constants for Weak
Monoprotic Acids and Bases
Substitute these values into the ionization constant
expression.
Kb
NH OH
4
1.8 10 5
NH3
1.8 10 5
2.3 10 2.3 10
3 3
x 2.3 10 3
141
Ionization Constants for Weak
Monoprotic Acids and 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 0.30M NH3
142
Solubility Product Constants
Ag Cl Ag aq Claq
143
Solubility Product Constants
K sp [Ag ][Cl ] 1.8 10 - -10
144
Solubility Product Constants
+ 2- H 2O
Ag2 S
100%
2 +
Ag + S 2-
145
Solubility Product Constants
Ksp Ag S 10. 10
2 2 49
146
Solubility Product Constants
H 2O
3 2 3
2+
Ca 3 PO4
3 Ca 2 PO4
2 s 100%
Ksp Ca 2 3
3 2
PO4 10 . 10 25
147
Solubility Product Constants
M r Ys s
H 2O
r M s
s Y r
100%
Ksp M Y
s r r s
148
Solubility Product Constants
2 1 3
CaNH4 PO 4s Ca aq NH4aq PO 4aq
K sp Ca 2 NH4 PO34
149
Determination of Solubility Product
Constants
Example 20-1: One liter of saturated silver chloride
solution contains 0.00192 g of dissolved AgCl at
25oC. Calculate the molar solubility of, and Ksp for,
AgCl.
The molar solubility can be easily calculated from
the data:
? mol AgCl 0.00192 g AgCl 1 mol AgCl
L L 143 g AgCl
5 mol AgCl
1.34 10
L
150
Determination of Solubility Product
Constants
The equation for the dissociation of silver chloride,
the appropriate molar concentrations, and the
solubility product expression are:
AgCl s Ag
Cl
1.34 10 M 1.34 10 M
-5 -5
Ksp Ag
Cl
151
Determination of Solubility Product
Constants
Substitution of the molar concentrations into the
solubility product expression gives:
134
. 10 134
. 10
5 5
10
18
. 10
152
Determination of Solubility Product
Constants
Example 20-2: One liter of saturated calcium
fluoride solution contains 0.0167 gram of CaF2 at
25oC. Calculate the molar solubility of, and Ksp
for, CaF2.
1. Calculate the molar solubility of CaF2.
153
Determination of Solubility Product
Constants
From the molar solubility, we can find the ion
concentrations in saturated CaF2. Then use those
values to calculate the Ksp.
Note: You are most likely to leave out the factor of 2 for the
concentration of the fluoride ion!
CaF
CaF22
Ca2+2
Ca
aq 2- F1-
+ 2F aq
4 4 4 4 4
.14
2.214 1010 MM2.214 10
.14 10M M 2(2(
2.214 10
.14 10M4 M
) )
K sp Ca F
2 2
2.14 10 4.28 10
4 4 2
3.92 10 11
154
Uses of Solubility
Product Constants
The solubility product constant can be used to
calculate the solubility of a compound at 25oC.
Example 20-3: Calculate the molar solubility of
barium sulfate, BaSO4, in pure water and the
concentration of barium and sulfate ions in
saturated barium sulfate at 25oC. For barium
sulfate, Ksp= 1.1 x 10-10.
155
Uses of Solubility
Product Constants
Make the algebraic substitution of x‟s into
solubility product expression and solve for x,
giving the ion concentrations.
5
x 1.0 10 M
Ba SO 1.0 10
2 2
4
5
M
156
Uses of Solubility
Product Constants
Finally, to calculate the mass of BaSO4 in 1.00 L
of saturated solution, use the definition of
molarity.
5
? g BaSO 4 1.0 10 mol 234 g
L L mol
3 g BaSO 4
2.3 10
L
157
Uses of Solubility
Product Constants
Example 20-4: The solubility product constant
for magnesium hydroxide, Mg(OH)2, is 1.5 x
10-11. Calculate the molar solubility of
magnesium hydroxide and the pH of a
saturated magnesium hydroxide solution at
25oC.
You do it!
158
Uses of Solubility
Product Constants
Be careful, do not forget the stoichiometric
coefficient of 2!
2
Mg(OH) 2 Mg aq 2 OH aq
xM xM 2 xM
Ksp Mg 2
OH 2
159
Uses of Solubility
Product Constants
Substitute the algebraic expressions into the
solubility product expression.
x 2 x 15
2
. 10 11
11
4 x 15
3
. 10
12
x 3.75 10
3
4
x 1.6 10 molar solubility
160
Uses of Solubility
Product Constants
Solve for the pOH and pH.
x 2 x 15
2
. 1011
. 1011
4 x 3 15
12
x 3.75 10
3
4
x 16
. 10 molar solubility
OH 2 M 3.2 10
- 4
M
pOH 3.49 pH 10.51
161
The Common Ion Effect in Solubility
Calculations
Example 20-5: Calculate the molar
solubility of barium sulfate, BaSO4, in
0.010 M sodium sulfate, Na2SO4, solution
at 25oC. Compare this to the solubility of
BaSO4 in pure water. (Example 20-3).
(What is the common ion? How was a
common ion problem solved in Chapter
19?)
162
The Common Ion Effect in Solubility
Calculations
1. Write equations to represent the equilibria.
2
Na 2SO 4
2 Na SO
1 0 0% +
4
xM xM xM
163
The Common Ion Effect in Solubility
Calculations
2. Substitute the algebraic representations of the
concentrations into the Ksp expression and
solve for x.
K sp Ba 2 SO 24 1.110 10
x 0.010 x
The simplifyin g assumption can be applied.
0.010 x 0.010
0.010 x = 1.110-10
x 1.110 8 molar solubility of BaSO 4
164
The Common Ion Effect in Solubility
Calculations
The molar solubility of BaSO4 in 0.010 M Na2SO4
solution is 1.1 x 10-8 M.
The molar solubility of BaSO4 in pure water is 1.0 x 10-
5 M.
166
The Reaction Quotient in
Precipitation Reactions
1. Write out the solubility expressions.
H 2O 100% 2
K2SO4
2 K +
SO4
Pb NO3 2 H 2 O 100%
Pb 2+
2 -
NO3
Will PbSO4 precipitate?
167
The Reaction Quotient in
Precipitation Reactions
Calculate the Qsp for PbSO4.
Assume that the solution volumes are additive.
Concentrations of the important ions are:
168
The Reaction Quotient in
Precipitation Reactions
Finally, calculate Qsp for PbSO4 and compare it to
the Ksp.
Qsp Pb 2
2
SO4
0.050 0.0050
4
2.5 10
8
Ksp 18
. 10 for PbSO 4
Qsp Ksp therefore solid forms
169
The Reaction Quotient in
Precipitation Reactions
Example 20-7: Suppose we wish to remove
mercury from an aqueous solution that contains
a soluble mercury compound such as Hg(NO3)2.
We can do this by precipitating mercury (II) ions
as the insoluble compound HgS. What
concentration of sulfide ions, from a soluble
compound such as Na2S, is required to reduce
the Hg2+ concentration to 1.0 x 10-8 M? For
HgS, Ksp=3.0 x 10-53.
You do it!
170
The Reaction Quotient in
Precipitation Reactions
HgS
Hg 2 S2
K sp Hg 2 S2 3.0 10 53
solve for S
2
S Hg
2
K sp
2
3.0 10 53
1.0 10 8
3.0 10 45
M
171
The Reaction Quotient in
Precipitation Reactions
Example 20-8: Refer to example 20-7. What
volume of the solution (1.0 x 10-8 M Hg2+ )
contains 1.0 g of mercury?
2
2 1 mol Hg 1.0 L
? L 1.0 g Hg 2
201 g Hg 1.0 10 8 mol Hg 2
5.0 105 L 125,000 gal
172
End of Lecture Unit 5
173
Unit Goals
174
CHM12-3
Lecture Unit 5
BASIC CHEMICAL AND IONIC EQUILIBRIA
175