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Lecture 14 Acids and Bases
Lecture 14 Acids and Bases
1
Acids
Have a sour taste. Vinegar owes its taste to acetic acid. Citrus
fruits contain citric acid.
H2
Bases
đắng
N H H N H
H H
acid base 4
Lewis Acids and Bases
F H F H
F B + F B
••
N H N H
F H F H
acid base
5
A Brønsted acid is a proton donor
A Brønsted base is a proton acceptor
6
Acid-Base Properties of Water
autoionization of water
+ -
H O + H O [H O H] + H O
H H H
conjugate
base
acid
H2O + H2O H3O+ + OH-
acid conjugate
7
base
The Ion Product of Water
[H+][OH-]
H2O (l) H+ (aq) + OH- (aq) Kc = [H2O] = constant
[H2O]
Kc[H2O] = Kw = [H+][OH-]
Solution Is
[H+] = [OH-] neutral
At 25 0C [H+] > [OH-] acidic
Kw = [H+][OH-] = 1.0 x 10-14
[H+] < [OH-] basic
8
What is the concentration of OH- ions in a HCl solution whose
hydrogen ion concentration is 1.3 M?
[H+] = 1.3 M
K 1 x 10 -14
w -15 M
[OH-] = = = 7.7 x 10
[H+] 1.3
9
pH – A Measure of Acidity
pH = -log [H+]
Solution is At 25 0C
neutral [H+] = [OH-] [H+] = 1 x 10-7 pH = 7
acidic [H+] > [OH-] [H+] > 1 x 10-7 pH < 7
basic [H+] < [OH-] [H+] < 1 x 10-7 pH > 7
pH [H+]
10
Other important relationships
pOH = -log [OH-]
pH + pOH = 14.00
11
Measure of pH
pH paper
pH meter
Red cabbage 12
Litmus paper
The pH of rainwater collected in a certain region of the
northeastern United States on a particular day was 4.82. What
is the H+ ion concentration of the rainwater?
pH = -log [H+]
[H+] = 10-pH = 10-4.82 = 1.5 x 10-5 M
13
Strong Electrolyte – 100% dissociation
H 2O
NaCl (s) Na+ (aq) + Cl- (aq)
15
Weak Bases are weak electrolytes
16
17
Strong Acid (HCl) Weak Acid (HF)
18
What is the pH of a 2 x 10-3 M HNO3 solution?
[H+][A-]
Ka =
[HA]
weak acid
Ka
strength
20
21
What is the pH of a 0.5 M HF solution (at 25 0C)?
[H+][F-]
HF (aq) H+ (aq) + F- (aq) Ka = = 7.1 x 10-4
[HF]
HF (aq) H+ (aq) + F- (aq)
Initial (M) 0.50 0.00 0.00
Change (M) -x +x +x
Equilibrium (M) 0.50 - x x x
x2
Ka = = 7.1 x 10-4 Ka << 1 0.50 – x 0.50
0.50 - x
x2
Ka = 7.1 x 10-4 x2 = 3.55 x 10-4 x = 0.019 M
0.50
[H+] = [F-] = 0.019 M pH = -log [H+] = 1.72
[HF] = 0.50 – x = 0.48 M 22
When can I use the approximation?
Ka << 1 0.50 – x 0.50
24
What is the pH of a 0.122 M monoprotic acid whose
Ka is 5.7 x 10-4?
HA (aq) H+ (aq) + A- (aq)
Initial (M) 0.122 0.00 0.00
Change (M) -x +x +x
Equilibrium (M) 0.122 - x x x
x2
Ka = = 5.7 x 10-4 Ka << 1 0.122 – x 0.122
0.122 - x
x2
Ka = 5.7 x 10-4 x2 = 6.95 x 10-5 x = 0.0083 M
0.122
26
Ionized acid concentration at equilibrium
percent ionization = x 100%
Initial concentration of acid
[H+]
Percent ionization = x 100% [HA]0 = initial concentration
[HA]0
27
Weak Bases and Base Ionization Constants
[NH4+][OH-]
Kb =
[NH3]
weak base
Kb
strength
28
29
Ionization Constants of Conjugate Acid-Base Pairs
KaKb = Kw
Kw Kw
Ka = Kb =
Kb Ka
30
Diprotic and Triprotic Acids
• May yield more than one hydrogen ion per molecule.
• Ionize in a stepwise manner; that is, they lose one proton at
a time.
• An ionization constant expression can be written for each
ionization stage.
• Consequently, two or more equilibrium constant expressions
must often be used to calculate the concentrations of
species in the acid solution.
31
32
Molecular Structure and Acid Strength
H X H+ + X-
The The
stronger weaker
the bond the acid
acidity
increases
33
34
Molecular Structure and Oxoacid Strength
d- d+
Z O H Z O- + H+
The O-H bond will be more polar and easier to break if:
• Z is very electronegative or
• Z is in a high oxidation state
35
Molecular Structure and Oxoacid Strength
••
••
O O
•• •• •• ••
••
••
H O Cl O H O Br O
•• •• • • •• •• • •
acidity
HClO3 > HBrO3 increases
36
Molecular Structure and Acid Strength
37
Acid-Base Properties of Salts
Neutral Solutions:
Salts containing an alkali metal or alkaline earth metal
ion (except Be2+) and the conjugate base of a strong
acid (e.g. Cl-, Br-, and NO3-).
H2O
NaCl (s) Na+ (aq) + Cl- (aq)
Basic Solutions:
Salts derived from a strong base and a weak acid.
H 2O
NaCH3COOH (s) Na+ (aq) + CH3COO- (aq)
38
Acid-Base Properties of Salts
Acid Solutions:
Salts derived from a strong acid and a weak base.
H2O
NH4Cl (s) NH4+ (aq) + Cl- (aq)
Al(H2O)3+
6 (aq) Al(OH)(H2O)52+(aq) + H+ (aq)
39
Acid Hydrolysis of Al3+
40
Acid-Base Properties of Salts
• Kb for the anion > Ka for the cation, solution will be basic
• Kb for the anion < Ka for the cation, solution will be acidic
• Kb for the anion Ka for the cation, solution will be neutral
41
42
Oxides of the Representative Elements
In Their Highest Oxidation States
44
Acid-Base Equilibria and
Solubility Equilibria
45
The common ion effect is the shift in equilibrium caused by the
addition of a compound having an ion in common with the
dissolved substance.
46
Consider mixture of salt NaA and weak acid HA.
NaA (s) Na+ (aq) + A- (aq) [H+][A-]
Ka =
HA (aq) H+ (aq) + A- (aq) [HA]
Ka [HA]
[H+] =
[A-] Henderson-Hasselbalch
equation
[HA]
-log [H+] = -log Ka - log
[A-] [conjugate base]
-] pH = pKa + log
[A [acid]
-log [H+] = -log Ka + log
[HA]
[A-]
pH = pKa + log pKa = -log Ka
[HA]
47
What is the pH of a solution containing 0.30 M HCOOH and
0.52 M HCOOK?
50
Which of the following are buffer systems? (a) KF/HF
(b) KBr/HBr, (c) Na2CO3/NaHCO3
51
Calculate the pH of the 0.30 M NH3/0.36 M NH4Cl buffer
system. What is the pH after the addition of 20.0 mL of 0.050
M NaOH to 80.0 mL of the buffer solution?
[NH3] [0.30]
pH = pKa + log pKa = 9.25 pH = 9.25 + log = 9.17
[NH4+] [0.36]
+]
0.028 0.025 [0.25]
[NH4 = [NH3] = pH = 9.25 + log = 9.20
0.10 0.10 [0.28] 52
Chemistry In Action: Maintaining the pH of Blood
53
Titrations (Review)
In a titration a solution of accurately known concentration is
added gradually added to another solution of unknown
concentration until the chemical reaction between the two
solutions is complete.
monitor pH
55
Strong Acid-Strong Base Titrations
NaOH (aq) + HCl (aq) H2O (l) + NaCl (aq)
56
Weak Acid-Strong Base Titrations
CH3COOH (aq) + NaOH (aq) CH3COONa (aq) + H2O (l)
CH3COOH (aq) + OH- (aq) CH3COO- (aq) + H2O (l)
At equivalence point (pH > 7):
CH3COO- (aq) + H2O (l) OH- (aq) + CH3COOH (aq)
57
Strong Acid-Weak Base Titrations
HCl (aq) + NH3 (aq) NH4Cl (aq)
H+ (aq) + NH3 (aq) NH4Cl (aq)
At equivalence point (pH < 7):
NH4+ (aq) + H2O (l) NH3 (aq) + H+ (aq)
58
Exactly 100 mL of 0.10 M HNO2 are titrated with a 0.10 M
NaOH solution. What is the pH at the equivalence point ?
60
Solutions of Red Cabbage Extract
pH
61
The titration curve of a strong acid with a strong base.
62
Which indicator(s) would you use for a titration of HNO2 with
KOH ?
63
Solubility Equilibria
66
What is the solubility of silver chloride in g/L ?
67
68
If 2.00 mL of 0.200 M NaOH are added to 1.00 L of 0.100 M
CaCl2, will a precipitate form?
69
What concentration of Ag is required to precipitate ONLY AgBr in
a solution that contains both Br- and Cl- at a concentration of
0.02 M?
AgCl AgBr
3.9 x 10-11 M < [Ag+] < 8.0 x 10-9 M
70
The Common Ion Effect and Solubility
What is the molar solubility of AgBr in (a) pure water and (b)
0.0010 M NaBr?
[CoCl42- ]
Kf =
Co(H2O)2+ [Co2+][Cl-]4
6 CoCl2-
4
stability of
Kf
HCl complex
73
Effect of Complexation on Solubility
AgNO
Add3 +
NHNaCl
3
AgCl 3)2+
Ag(NH 74
75
76
Qualitative
Analysis of
Cations
77
Flame Test for Cations
78
Chemistry In Action: How an Eggshell is Formed
electron micrograph
79