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Equilibria
Agenda
Formal vs equilibrium concentration
Acid equilibria
Base equilibria
Ka, Kb and Kw
Common ion effect
Buffers
Acid-Base Titrations
Note to Students
This chapter is considered the hardest in CHY102.
Coverage
Sections you should know:
16.2 Buffers: Solutions That Resist pH Change
16.3 Buffer Effectiveness: Buffer Range and Buffer Capacity
16.4 Titrations and pH Curves
Things to exclude:
16.1 The Danger of Antifreeze
16.5 Solubility Equilibria and the Solubility Product Constant
16.6 Precipitation
16.7 Qualitative Chemical Analysis
16.8 Complex-Ion Equilibria
Formal and
equilibrium
concentrations
Acid examples
e.g. Strong acid: 1.0 molL-1 HCl (formal) is
really
conc.) is
Base examples
e.g. Strong base: 1.0 molL-1 NaOH (formal) is
really
conc.) is
HF(aq)+H2O(l)
A.
B.
C.
D.
H3O+(aq)+F(aq)
Acid equilibria
10
Acid dissociation
constant, Ka
11
Note on abbreviations
Generic weak acid: HA
HA = acid
A- = conjugate base (anion)
Acetic acid: CH3COOH
HOAc = CH3COOH
acetic acid
OAc- = CH3COO-
Ac = CH3CO-
12
Getting Ka from pH
e.g. The pH of a soln of acetic acid with a
OAc H
HOAc
13
Regarding H+
Actually two sources of H+
Water dissociation: H2O(l) H+(aq) + OH-(aq)
HOAc dissociation: HOAc(l) H+(aq) + OAc-(aq)
Total [H+] = [OAc-] + [OH-] (by charge balance)
Construct Equilibrium
Table
HOAc(aq)
I
OAc(aq)+H+(aq)
0.020
C
E
Formal concentration of HOAc is 0.020 mol/L
It will serve as the initial concentration (formally)
15
Construct Equilibrium
Table
HOAc(aq)
I
0.020
OAc(aq)+H+(aq)
0
C
E
Using the same formalism, initial H+ and OAcconcentrations are initially zero
16
Construct Equilibrium
Table
HOAc(aq)
I
C
E
0.020
OAc(aq)+H+(aq)
0
0
5.8910-4
Construct Equilibrium
Table
HOAc(aq)
I
0.020
C
E
-5.8910-4
0.0194
OAc(aq)+H+(aq)
0
+5.8910-4
5.8910-4
0
+5.8910-4
5.8910-4
Calculate Ka
OAc H 5.89 10 5.89 10
Ka
HOAc
0.0194
= 1.810-5
19
Percent Ionization
20
Concentration and % I
%I depends on both Ka and cHA
[H+] increases with cHA
But %I decreases
21
Example
At equilibrium, [H+] = [A-] = x and [HA] = cHA x
Ka
H A
HA
x2
c HA x
x 2 K a x - c HA K a 0
K a K a 4c HA K a
x
2
2
pH
% Ionisation
23
0.010%
0.10%
1.0%
10%
24
26
6.810-4
x K a x 0.035K a 0
2
K a K a2 4(0.035) K a
x
4.55 10 3
2
(D)
27
NOTE: Simplifying
assumption
If x << 0.035, then 0.035-x 0.035
Equilibrium expression then becomes
Ka
H F
HF
x2
6.8 10 4
0.035
0.035 6.8 10
4.87 10
(C)
28
Checking Assumption
Rule of thumb: If [H+] > 0.05cHA, use
quadratic formula
cHA
0.035
answer
29
Base equilibria
30
Base Dissociation
Constant, Kb
Bq is a weak base with a charge q = 0,-1,-2,-3
[HBq 1 ][OH ]
Kb
[Bq ]
31
Base Dissociation
Constant, Kb
32
pH of a Weak Base
33
pH of a Weak Base
What is pH of 5.0% NaClO? (Kb=3.310-7;
=1.07 g/mL)
Convert 5.0 % NaClO into molL-1
5.0gNaClO 1molNaClO
1.07gsoln
100gsoln
74.4gNaClO 1.00 10 3 Lsoln
pH of a Weak Base
ClO(aq)+H2O(l)
I
C
0.719
-x
0.719 - x
----
HClO(aq)+OH(aq)
0
+x
0
+x
[HClO][OH ]
x2
7
Kb
3.3
10
0.719 x
[ClO ]
35
pH of a Weak Base
Using the quadratic formula,
7
7 2
3.3 10 3.3 10 40.7193.3 10 7
x
2
x = 4.8610-4 mol L-1 = [OH-]
Want pH, so find [H+]
[OH-][H+] = Kw = 1.010-14
[H+] = (1.010-14)/(4.8610-4) = 2.0510-11 mol L-1
pH = -log[H+] = -log(2.0510-11) = 10.69
36
Ka, Kb and Kw
37
Relationship Between Ka
and Kb
KaKb = Kw
H A OH HA
KaKb
HA
A
= [OH-][H+] = Kw
conjugate base
38
CO32-?
Kb = Kw/Ka = (1.010-14)/(5.610-11)
= 1.810-4
39
LC: Ka and Kb
Ka for HCN is 4.910-10 at 25 C. Calculate Kb for
CN-.
A.
B.
C.
D.
2.910-5
4.910-5
2.010-5
2.010-9
40
LC: Ka and Kb
Ka for HCN is 4.910-10 at 25 C. Calculate Kb for
CN-.
C. 2.010-5
Kb = Kw/Ka = 1.010-14/4.910-10
= 2.040810-5 = 2.010-5
41
42
43
44
Example
%I of 0.100 mol/L HOAc (Ka=1.810-5) is 1.3% in
water. What is it in 0.100 M NaOAc? (NaOAc
completely dissociates.)
45
0.100
H+(aq)+OAc(aq)
0
0.100
C
E
cHOAc = 0.100 mol/L
cOAc- = 0.100 mol/L (from NaOAc)
Initial conc. of H+ formally zero
46
H+(aq)+OAc(aq)
0.100
0.100
C
E
-x
+x
+x
H+(aq)+OAc(aq)
0.100
0.100
C
E
-x
+x
+x
0.100 + x
0.100 - x
48
1.8 10
0.100 x
[HOAc]
Assuming x<<0.100,
x = 1.810-5 = [H+]
%I = 0.018% (compare: 1.3% in water)
Adding OAc- shifts equilib towards reactants
49
Buffers
The previous example was a buffer
In this section well learn what they are and an easier
way to calculate their pH
50
Buffers
The previous example was a buffer
In this section well learn
What a buffer is and what it does
How its made
How it works
And an easier way to calculate its pH
51
Buffer
Solution that resists changes in pH upon
base
Preparation (3 methods)
Mix weak acid with a salt of its conjugate base
52
Adding OH- consumes HA, produces AResults in smaller pH rise than expected
Selecting a Buffer
Buffers are most effective when [HA] = [A -]
Rearranging Ka
[HA]
[H ] K a
[A ]
interest
55
56
Henderson-Hasselbalch Equation
A convenient way to calculate pH of buffer:
H K
HA
HA
logH log K a
A
HA
57
Henderson-Hasselbalch Equation
If % ionization is small, then
[HA] ca
(a stands for acid)
[A-] cb
(b stands for base)
pH pK a log
ca
Using HendersonHasselbalch
What is the pH of a solution that is formally
pH pK a log
ca
0.10
pH 9.251 log
9.07
0.15
59
Check assumptions
Is NH4+ appreciably dissociated?
[H+] = 10-9.07 = 8.510-10
% ionization = (8.510-10/0.15)100% << 1%
Is NH3 appreciably hydrolysed?
LC: HendersonHasselbalch
What is the pH of a buffer solution that is 0.10
mol/L in acetic acid and 0.50 mol/L in sodium
acetate?
Ka = 1.810-5
A.
B.
C.
D.
2.87
4.05
4.74
5.44
61
LC: Henderson-Hasselbalch
What is the pH of a buffer solution that is 0.10
mol/L in acetic acid and 0.50 mol/L in sodium
acetate?
Ka = 1.810-5
cb
pH pK a log
D. 5.44
ca
62
Creating a buffer
e.g. What mass of NaOAc (82.0 g/mol) would
pH pK a log
ca
ca
pH
K a ca
cb pH
10
63
Creating a buffer
1.8 10 0.25
0.45
5
cb
1.0 10 5
64
The stoichiometric
calculation
What reacts with HCl?
HCl (aq) + NH3 (aq) NH4Cl (aq)
Moles NH3 before reaction:
(0.50 mol/L)(0.500 L) = 0.25 mol
66
The stoichiometric
calculation
During rxn, HCl completely consumed to form
NH4+
Moles after rxn,
moles NH3 = 0.25 mol - 0.10 mol = 0.15
mol
moles NH4+ = 0.15 mol + 0.10 mol = 0.25
mol
moles HCl = 0
67
Dilution calculation
Formal concs after rxn
68
Henderson-Hasselbalch
calc
cb
pH pK a log
ca
0.214
pH 9.251 log
9.03
0.357
69
Acid-Base
Titrations
70
Acid-Base Titrations
Analyte is acid and titrant a base, or vice
versa
Analyte may be weak or strong
Titrant is always strong
We will calculate the titration curve for two
types of titration:
strong acid (analyte) titrated with a strong
base, and
weak acid (analyte) titrated with a strong base
71
Titration Curves
Graph of pH vs
volume of titrant
added
Equivalence point is the
inflection point
The end point
determined by indicator
Indicator chosen to
change colour at the
equivalence point
72
Titration
error
73
acids
Due to incomplete dissociation
indicator
74
75
76
Summary
Understand formal vs equilibrium
concentration
Know how to set up and solve
Weak acid equilibria
Weak base equilibria
titrations
Slides 78-98 (following)
77
Suggested practice
problems
Review questions 2 19
Problems by topic 29, 33, 37, 41, 45, 47, 49,
53, 55, 59, 61, 65, 67, 69, 71, 75, 77, 79, 81,
87159, 161
78
Self-study
Calculating
titration curves
Self-study section
A nice application of acid-base equilibrium
calculations
79
Self-study
80
Self-study
Self-study
Region 1: Initial pH
Initial pH means pH before any NaOH added
[H+] = cHCl
HCl is a strong acid
All the HCl is dissociated in water
82
Self-study
Region 2: Equivalence
point
83
Self-study
Region 2: Equivalence
point
84
Self-study
85
Self-study
= 1.010-4 mol/L
pH = -log(1.010-4) = 4.00
Plot a point at
(VNaOH = 49.90 mL, pH = 4.00)
86
Self-study
Region 5: PostEquivalence
Self-study
V
pH of titrant is 14.00 + log(0.100) = 13.00
pH should not rise above 13.00
88
Self-study
The pH Curve
14
12
pH
10
8
6
4
2
0
0
10
20
30
40
50
60
70
Example 2: Weak
acid titrated with
strong base
Self-study
90
Self-study
example
91
Self-study
Self-study
Region 1: Initial pH
pH is found from an equilibrium calculation
[A ][H ]
Ka
1.8 10 5
[HA]
If a conc, x, of HA dissociates, then
x2
Ka
1.8 10 5
0.100 x
If x << 0.100, then
x 1.8 10 5 0.100 -31.34 10 3
And so the pH = -log(1.3410 ) = 2.87 (VNaOH =
0)
93
Self-study
Region 2: Equivalence
94
Self-study
Region 2: Equivalence
Perform a Kb calculation to find [OH-]
[HOAc][OH ] K w
10
Kb
5.6
10
[OAc ]
Ka
If x mol/L of OAc- react with water, then
x2
Kb
5.6 10 10
0.0500 x
x = 5.2910-6 = [OH-], so pOH = 5.28
pH = 14.00 - 5.28 = 8.72
(basic, as expected)
95
Self-study
x0.04995 x
5
Ka
1.8
10
4
1.0
10
x x = 3.610-8
Solving (assume x<<0.0001):
pH = -log(3.610-8) = 7.44
96
Self-study
Self-study
(25.00 mL)
Half HOAc consumed (now OAc-)
Solution is a buffer
Use Henderson-Hasselbalch
cb equation
pH pK a log
ca
cb = ca, so pH = pKa = -log(1.810-5) = 4.74
Plot point at (25.00 mL, 4.74)
98
Self-study
Comparison of titration
curves
14
12
10
pH
8
6
2
0
0
10
20
30
40
50
60
70