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Transcript of Acids and Bases Chapter 15 Copyright © The McGraw-Hill Companies, Inc. Permission required for...
Acids and Bases
Chapter 15
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
1) Compare and contrast Arrhenius, Brønsted, and Lewis acids
and bases.
2) Describe what is meant by conjugate acid-base pairs and
give several examples.
3) Use Kw to determine [H+] and [OH-] of solutions.
4) Discuss the pH scale and calculate pH and pOH given either
[H+] or [OH-].
5) Define strong and weak acids and bases and give several
examples of each.
6) Relate properties of conjugate acid-base pairs.
7) Determine Ka from experimental data.
8) Calculate pH, [H+] , weak acid concentration, and conjugate base
concentration given Ka and the initial concentration of the weak
acid using the quadratic equation or the method of successive
approximation as needed.
9) Calculate percent ionization for a weak acid needed.
10) Calculate pH, [OH-], weak base concentration, and conjugate acid
concentration given Kb and the initial concentration of the weak
base using the quadratic equation or the method of successive
approximation
11) Show the relationship between Ka,, Kb, and Kw.
12) Calculate concentrations of all species present at equilibrium for
diprotic and polyprotic acids.
13) Relate molecular structure and the strength of acids.
14) Predict the relative strengths of oxoacids.
15) Describe salt hydrolysis and explain how some salts produce
neutral solutions, some acidic solutions and others basic solutions.
16) Calculate the pH of salt solutions and determine the percent
hydrolysis.
17) Describe acid-base properties of oxides and hydroxides.
18) Give several examples of Lewis acid-base reactions.
Acids
Have a sour taste. Vinegar owes its taste to acetic acid. Citrusfruits contain citric acid.
React with certain metals to produce hydrogen gas.
React with carbonates and bicarbonates to produce carbon dioxide gas
Have a bitter taste.
Feel slippery. Many soaps contain bases.
Bases
4.3
Arrhenius acid is a substance that produces H+ (H3O+) in water
Arrhenius base is a substance that produces OH- in water
4.3
Copyright ©2001 by Harcourt, Inc. All rights reserved.
Brønsted-Lowry Model of Acids and Bases
Acid is proton donor, base is proton acceptor
HB(aq)+A-(aq) HA(aq)+B-(aq)
HB, HA are acids; A-, B-are bases. HB –B-and HA –A-are conjugate acid-base pairs.
Copyright © 2001 by Harcourt, Inc. All rights reserved.
Acidic and Basic Water Solutions
Aqueous solution
pH
Copyright ©2001 by Harcourt, Inc. All rights reserved.
Aqueous solution
In any aqueous solution, there is an equilibrium between H30+
(H+) ions and OH–ions:
H2O H+(aq) + OH–(aq)
KW = [H+] ́ [OH–] = 1.0 ́ 10-14 at 25°C
1. Pure water: [H+] = [OH–] = 1.0 ́ 10–7 M; neutral solution
2. Acidic solution: [H+] > 1.0 ́ 10–7 M> [OH–]
3. Basic solution: [OH–] > 1.0 ́ 10–7 M> [H+]In seawater, [H+] = 5 ́ 10-9 M; [OH–] = ?[OH–] = (1.0 ́ 10-14) / (5 ́ 10-9) = 2 ́ 10-6 M
Copyright © 2001 by Harcourt, Inc. All rights reserved.
pH
pH = –1og10[H+]
Neutral solution: pH = 7.0
Acidic solution: pH < 7.0
Basic solution: pH > 7.0Suppose [H+] = 2.4 ´10-6 M; calculate pH
pH = –1og10(2.4 ´10–6) = 5.62
Suppose pH = 8.68; calculate [H+]
[H+] = 10–8.68 = 2.1 ´10–9 M
pOH = –1og10[OH–]; pH + pOH = 14.00 at 25°C
A Brønsted acid is a proton donorA Brønsted base is a proton acceptor
acidbase acid base
15.1
acidconjugate
basebase conjugate
acid
O
H
H + O
H
H O
H
H H OH-+[ ] +
Acid-Base Properties of Water
H2O (l) H+ (aq) + OH- (aq)
H2O + H2O H3O+ + OH-
acid conjugate
base
base conjugate
acid
15.2
autoionization of water
H2O (l) H+ (aq) + OH- (aq)
The Ion Product of Water
Kc =[H+][OH-]
[H2O][H2O] = constant
Kc[H2O] = Kw = [H+][OH-]
The ion-product constant (Kw) is the product of the molar concentrations of H+ and OH- ions at a particular temperature.
At 250CKw = [H+][OH-] = 1.0 x 10-14
[H+] = [OH-]
[H+] > [OH-]
[H+] < [OH-]
Solution Is
neutral
acidic
basic
15.2
What is the concentration of OH- ions in a HCl solution whose hydrogen ion concentration is 1.3 M?
Kw = [H+][OH-] = 1.0 x 10-14
[H+] = 1.3 M
[OH-] =Kw
[H+]
1 x 10-14
1.3= = 7.7 x 10-15 M
15.2
pH – A Measure of Acidity
pH = -log [H+]
[H+] = [OH-]
[H+] > [OH-]
[H+] < [OH-]
Solution Is
neutral
acidic
basic
[H+] = 1 x 10-7
[H+] > 1 x 10-7
[H+] < 1 x 10-7
pH = 7
pH < 7
pH > 7
At 250C
pH [H+]
15.3
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 = 1.51 x 10-5 M
The OH- ion concentration of a blood sample is 2.5 x 10-7 M. What is the pH of the blood?
pH + pOH = 14.00
pOH = -log [OH-] = -log (2.5 x 10-7) = 6.60
pH = 14.00 – pOH = 14.00 – 6.60 = 7.40
15.3
Strong Electrolyte – 100% dissociation
NaCl (s) Na+ (aq) + Cl- (aq)H2O
Weak Electrolyte – not completely dissociated
CH3COOH CH3COO- (aq) + H+ (aq)
Strong Acids are strong electrolytes
HCl (aq) + H2O (l) H3O+ (aq) + Cl- (aq)
HNO3 (aq) + H2O (l) H3O+ (aq) + NO3- (aq)
HClO4 (aq) + H2O (l) H3O+ (aq) + ClO4- (aq)
H2SO4 (aq) + H2O (l) H3O+ (aq) + HSO4- (aq)
15.4
HF (aq) + H2O (l) H3O+ (aq) + F- (aq)
Weak Acids are weak electrolytes
HNO2 (aq) + H2O (l) H3O+ (aq) + NO2- (aq)
HSO4- (aq) + H2O (l) H3O+ (aq) + SO4
2- (aq)
H2O (l) + H2O (l) H3O+ (aq) + OH- (aq)
Strong Bases are strong electrolytes
NaOH (s) Na+ (aq) + OH- (aq)H2O
KOH (s) K+ (aq) + OH- (aq)H2O
Ba(OH)2 (s) Ba2+ (aq) + 2OH- (aq)H2O
15.4
F- (aq) + H2O (l) OH- (aq) + HF (aq)
Weak Bases are weak electrolytes
NO2- (aq) + H2O (l) OH- (aq) + HNO2 (aq)
Conjugate acid-base pairs:
• The conjugate base of a strong acid has no measurable strength.
• H3O+ is the strongest acid that can exist in aqueous solution.
• The OH- ion is the strongest base that can exist in aqeous solution.
15.4
What is the pH of a 2 x 10-3 M HNO3 solution?
HNO3 is a strong acid – 100% dissociation.
HNO3 (aq) + H2O (l) H3O+ (aq) + NO3- (aq)
pH = -log [H+] = -log [H3O+] = -log(0.002) = 2.70
Start
End
0.002 M
0.002 M 0.002 M0.0 M
0.0 M 0.0 M
What is the pH of a 1.8 x 10-2 M Ba(OH)2 solution?
Ba(OH)2 is a strong base – 100% dissociation.
Ba(OH)2 (s) Ba2+ (aq) + 2OH- (aq)
Start
End
0.018 M
0.018 M 0.036 M0.0 M
0.0 M 0.0 M
pH = 14.00 – pOH = 14.00 + log(0.036) = 12.5615.4
HA (aq) + H2O (l) H3O+ (aq) + A- (aq)
Weak Acids (HA) and Acid Ionization Constants
HA (aq) H+ (aq) + A- (aq)
Ka =[H+][A-][HA]
Ka is the acid ionization constant
Ka
weak acidstrength
15.5
Copyright © 2001 by Harcourt, Inc. All rights reserved.
Calculation of [H+] in solution example
Find [H+] in 0.200 M HC2H3O2, Ka=1.8 ´10–5
Let [H+] = x, then [C2H3O2–] = x,
[HC2H3O2] = 0.200 – x
= 1.8 ´10–5
Assume 0.200 - x 0.200 ; x = 1.9 ´10–3 M
In this case, % ionization = ´100 = 1.0%
x2
0.200 – x
1.9 ´10–3
0.200
What is the pH of a 0.5 M HF solution (at 250C)?
HF (aq) H+ (aq) + F- (aq) Ka =[H+][F-][HF]
= 7.1 x 10-4
HF (aq) H+ (aq) + F- (aq)
Initial (M)
Change (M)
Equilibrium (M)
0.50 0.00
-x +x
0.50 - x
0.00
+x
x x
Ka =x2
0.50 - x= 7.1 x 10-4
Ka x2
0.50= 7.1 x 10-4
0.50 – x 0.50Ka << 1
x2 = 3.55 x 10-4 x = 0.019 M
[H+] = [F-] = 0.019 M pH = -log [H+] = 1.72
[HF] = 0.50 – x = 0.48 M15.5
When can I use the approximation?
0.50 – x 0.50Ka << 1
When x is less than 5% of the value from which it is subtracted.
x = 0.0190.019 M0.50 M
x 100% = 3.8%Less than 5%
Approximation ok.
What is the pH of a 0.05 M HF solution (at 250C)?
Ka x2
0.05= 7.1 x 10-4 x = 0.006 M
0.006 M0.05 M
x 100% = 12%More than 5%
Approximation not ok.
Must solve for x exactly using quadratic equation or method of successive approximation. 15.5
Solving weak acid ionization problems:
1. Identify the major species that can affect the pH.
• In most cases, you can ignore the autoionization of water.
• Ignore [OH-] because it is determined by [H+].
2. Use ICE to express the equilibrium concentrations in terms of single unknown x.
3. Write Ka in terms of equilibrium concentrations. Solve for x by the approximate method. If approximation is not valid, solve for x exactly.
4. Calculate concentration of all species and/or pH of the solution.
15.5
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)
Change (M)
Equilibrium (M)
0.122 0.00
-x +x
0.122 - x
0.00
+x
x x
Ka =x2
0.122 - x= 5.7 x 10-4
Ka x2
0.122= 5.7 x 10-4
0.122 – x 0.122Ka << 1
x2 = 6.95 x 10-5 x = 0.0083 M
0.0083 M0.122 M
x 100% = 6.8%More than 5%
Approximation not ok.
15.5
Ka =x2
0.122 - x= 5.7 x 10-4 x2 + 0.00057x – 6.95 x 10-5 = 0
ax2 + bx + c =0-b ± b2 – 4ac
2ax =
x = 0.0081 x = - 0.0081
HA (aq) H+ (aq) + A- (aq)
Initial (M)
Change (M)
Equilibrium (M)
0.122 0.00
-x +x
0.122 - x
0.00
+x
x x
[H+] = x = 0.0081 M pH = -log[H+] = 2.09
15.5
percent ionization = Ionized acid concentration at equilibrium
Initial concentration of acidx 100%
For a monoprotic acid HA
Percent ionization = [H+]
[HA]0
x 100% [HA]0 = initial concentration
15.5
Copyright © 2001 by Harcourt, Inc. All rights reserved.
Weak Bases
Molecules
Anions derived from weak acids
Copyright ©2001 by Harcourt, Inc. All rights reserved.
Anions derived from weak acids
F–(aq) + H2O HF(aq) + OH–(aq)
Copyright © 2001 by Harcourt, Inc. All rights reserved.
Weak Bases
Equilibrium constant
•Expression for Kb
•Relation between Ka and Kb
•Calculation of [OH–] in solution of weak base
NH3 (aq) + H2O (l) NH4+ (aq) + OH- (aq)
Weak Bases and Base Ionization Constants
Kb =[NH4
+][OH-][NH3]
Kb is the base ionization constant
Kb
weak basestrength
15.6
Solve weak base problems like weak acids except solve for [OH-] instead of [H+].
15.7
Ionization Constants of Conjugate Acid-Base Pairs
HA (aq) H+ (aq) + A- (aq)
A- (aq) + H2O (l) OH- (aq) + HA (aq)
Ka
Kb
H2O (l) H+ (aq) + OH- (aq) Kw
KaKb = Kw
Weak Acid and Its Conjugate Base
Ka = Kw
Kb
Kb = Kw
Ka
Copyright © 2001 by Harcourt, Inc. All rights reserved.
Relation between Ka and Kb
Ka ´Kb = KW = 1.0 ´10–14
Ka Kb
HF 6.9 ´10–4 F– 1.4 ´10–11
HAc 1.8 ´10–5 Ac– 5.6 ´10–10
NH4+ 5.6 ´10–10 NH3 1.8 ´10–5
Strength of base is inversely related to that of conjugate weak acid.
Copyright © 2001 by Harcourt, Inc. All rights reserved.
Calculation of [OH–] in solution of weak base
= 1.4 ´10–11 ; = 1.4 ´10–11
[OH–] = 1.2 ´10–6 M ; pH = 8.08
[HF][OH–][F–]
[OH–]2
0.10
Molecular Structure and Acid Strength
H X H+ + X-
The stronger the bond
The weaker the acid
HF << HCl < HBr < HI
15.9
Molecular Structure and Acid Strength
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
15.9
Molecular Structure and Acid Strength
1. Oxoacids having different central atoms (Z) that are from the same group and that have the same oxidation number.
Acid strength increases with increasing electronegativity of Z
H O Cl O
O••
••••••
••
••••
••••
H O Br O
O••
••••••
••
••••
••••Cl is more electronegative than Br
HClO3 > HBrO3
15.9
Molecular Structure and Acid Strength
2. Oxoacids having the same central atom (Z) but different numbers of attached groups.
Acid strength increases as the oxidation number of Z increases.
HClO4 > HClO3 > HClO2 > HClO
15.9
Acid-Base Properties of SaltsNeutral 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
-).
NaCl (s) Na+ (aq) + Cl- (aq)H2O
Basic Solutions:
Salts derived from a strong base and a weak acid.
NaCH3COOH (s) Na+ (aq) + CH3COO- (aq)H2O
CH3COO- (aq) + H2O (l) CH3COOH (aq) + OH- (aq)
15.10
Acid-Base Properties of Salts
Acid Solutions:
Salts derived from a strong acid and a weak base.
NH4Cl (s) NH4+ (aq) + Cl- (aq)
H2O
NH4+ (aq) NH3 (aq) + H+ (aq)
Salts with small, highly charged metal cations (e.g. Al3+, Cr3+, and Be2+) and the conjugate base of a strong acid.
Al(H2O)6 (aq) Al(OH)(H2O)5 (aq) + H+ (aq)3+ 2+
15.10
Acid-Base Properties of Salts
Solutions in which both the cation and the anion hydrolyze:
• 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
15.10
Arrhenius acid is a substance that produces H+ (H3O+) in water
A Brønsted acid is a proton donor
A Lewis acid is a substance that can accept a pair of electrons
A Lewis base is a substance that can donate a pair of electrons
Definition of An Acid
H+ H O H••••
+ OH-••••••
acid base
N H••
H
H
H+ + N H
H
H
H
acid base15.12
Lewis Acids and Bases
N H••
H
H
acid base
F B
F
F
+ F B
F
F
N H
H
H
No protons donated or accepted!
15.12