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Acids
4.3
A Brønsted acid is a proton donor
A Brønsted base is a proton acceptor
15.1
Monoprotic acids
HCl H+ + Cl- Strong electrolyte, strong acid
Diprotic acids
H2SO4 H+ + HSO4- Strong electrolyte, strong acid
Triprotic acids
H3PO4 H+ + H2PO4- Weak electrolyte, weak acid
H2PO4- H+ + HPO42- Weak electrolyte, weak acid
HPO42- H+ + PO43- Weak electrolyte, weak acid
5
6
Identify each of the following species as a Brønsted acid, base,
or both. (a) HI, (b) CH3COO-, (c) H2PO4-
7
A Lewis acid is a substance that can accept a pair of electrons
15.12
Neutralization Reaction
9
Neutralization Reaction Involving a Weak
Electrolyte
10
Neutralization Reaction Producing a Gas
11
Acid-Base Properties of Water
autoionization of water
+ -
H O + H O
[ H O H
] + H O
H H H
[H+][OH-]
H2O (l) H+ (aq) + OH- (aq) Kc = [H2O] = constant
[H2O]
Kc[H2O] = Kw = [H+][OH-]
Solution Is
[H+] = [OH-] neutral
At 250C [H+] > [OH-] acidic
Kw = [H+][OH-] = 1.0 x 10-14
[H+] < [OH-] basic
15.2
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
15.2
pH – A Measure of Acidity
pH = -log [H+]
Solution Is At 250C
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+]
15.3
pOH = -log [OH-]
pH + pOH = 14.00
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 = 1.5 x 10-5 M
15.3
Strong Electrolyte – 100% dissociation
H 2O
NaCl (s) Na+ (aq) + Cl- (aq)
15.4
Weak Bases are weak electrolytes
15.4
15.4
Strong Acid Weak Acid
15.4
What is the pH of a 2 x 10-3 M HNO3 solution?
HNO3 is a strong acid – 100% dissociation.
Start 0.002 M 0.0 M 0.0 M
HNO3 (aq) + H2O (l) H3O+ (aq) + NO3- (aq)
End 0.0 M 0.002 M 0.002 M
[H+][A-]
Ka =
[HA]
weak acid
Ka
strength
15.5
15.5
What is the pH of a 0.5 M HF solution (at 250C)?
[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
15.5
When can I use the approximation?
Ka << 1 0.50 – x 0.50
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) 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
0.0083 M More than 5%
x 100% = 6.8%
0.122 M Approximation not ok.
15.5
x2
Ka = = 5.7 x 10-4 x2 + 0.00057x – 6.95 x 10-5 = 0
0.122 - x
-b ± b2 – 4ac
ax2 + bx + c =0 x=
2a
x = 0.0081 x = - 0.0081
15.5
Ionized acid concentration at equilibrium
percent ionization = x 100%
Initial concentration of acid
[H+]
Percent ionization = x 100% [HA]0 = initial concentration
[HA]0
15.5
Weak Bases and Base Ionization Constants
[NH4+][OH-]
Kb =
[NH3]
weak base
Kb
strength
15.6
15.6
Ionization Constants of Conjugate Acid-Base Pairs
KaKb = Kw
Kw Kw
Ka = Kb =
Kb Ka
15.7
15.8
Molecular Structure and Acid Strength
H X H+ + X-
The The
stronger weaker
the bond the acid
15.9
Molecular Structure and Acid 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
15.9
Molecular Structure and Acid Strength
••
••
O O
•• •• •• ••
••
••
H O Cl O H O Br O
• • • • •• • • • • ••
15.9
Molecular Structure and Acid Strength
15.9
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-).
H 2O
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)
15.10
Acid-Base Properties of Salts
Acid Solutions:
Salts derived from a strong acid and a weak base.
H 2O
NH4Cl (s) NH4+ (aq) + Cl- (aq)
Al(H2O)3+
6 (aq) Al(OH)(H2O)52+(aq) + H+ (aq)
15.10
Acid Hydrolysis of Al3+
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
Oxides of the Representative Elements
In Their Highest Oxidation States
CO2 (g) + H2O (l) H2CO3 (aq) N2O5 (g) + H2O (l) 2HNO3 (aq)
15.11
A buffer solution is a solution of:
1. A weak acid or a weak base and
2. The salt of the weak acid or weak base
Both must be present!
16.3
HCl H+ + Cl-
HCl + CH3COO- CH3COOH + Cl-
16.3
Which of the following are buffer systems? (a) KF/HF
(b) KBr/HBr, (c) Na2CO3/NaHCO3
16.3
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]