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Chapter4-Kesetimbangan Asam Basa
Chapter4-Kesetimbangan Asam Basa
in Aqueous Solutions
Chapter 4
Kimia Dasar II (CH1201)
2019-2020
References:
Brady, J, E., Jepersen, N. D., Hyslop A., 2012, Chemistry, 7th Edition, International Student Version, John Wiley and Sons.
Raymond Chang and Kenneth A. Goldsby, 2012, Chemistry, McGraw-Hill
MITopencourseware
Brady/Jespersen/Hyslop, Chemistry7E, Copyright © 2015 John Wiley & Sons, Inc. All Rights Reserved.
Contents
1. Ionization Constant, Ka and Kb
2. Determining Ka and Kb Values
3. pH of Weak Acid and Weak Base Solutions
4. Acid-Base Properties of Salt Solution
5. Buffer Solution
6. Polyprotic Acids
7. Acid-Base Titration
2
Contents
1. Ionization Constant, Ka and Kb
2. Determining Ka and Kb Values
3. pH of Weak Acid and Weak Base Solutions
4. Acid-Base Properties of Salt Solution
5. Buffer Solution
6. Polyprotic Acids
7. Acid-Base Titration
3
Ionization of Water and pH Concept
4
Weak Acids and Bases
• Incompletely ionized
• Molecules and ions exist in equilibrium
7
Table 16.2. Weak Monoprotic Acids at
25 °C
8
Reaction of a Weak Base with Water
CH3COO–(aq) + H2O CH3COOH(aq) + OH–(aq)
NH3(aq) + H2O NH4+(aq) + OH–(aq)
or generally
9
Table 16.3. Weak Bases at 25 °C
10
Learning Check
What is the pKa of HF if Ka = 3.5 × 10–4?
= 3.5 × 10–4
= 1.7 × 10–9
12
Conjugate Acid-Base Pairs and
Values of Ka and Kb
1. Consider ionization reaction of generic acid
and water
HA(aq) + H2O A–(aq) + H3O+(aq)
13
3. Now adding reactions we get
15
1. Calculating Ka and Kb from Initial
Concentrations and Equilibrium Data
• Need to evaluate mass action expression = reaction
quotient Q when the reaction is at equilibrium
• Since Q = Kc when at equilibrium
• Can either be given initial concentrations and one
equilibrium concentration
• Usually pH or pOH
• OR can be given initial concentrations and
% ionization
16
Calculating Ka
• Niotinic acid (niacin) is a monoprotic acid with the
formula HC6H4NO2. A solution that is 0.012 M in
nicotinic acid has a pH of 3.39 at 25 °C. What are
the acid-ionization constant, Ka, and pKa for this
acid at 25 °C?
• What is the degree of ionization of nicotinic acid
in this solution?
17
Calculating Ka (cont.)
• Next calculate:
20
2. Calculating Equilibrium Concentrations from
Ka (or Kb) and Initial Concentrations
21
Your Turn!
Hypochlorous acid, HClO, is a weak acid with
Ka = 3.0 × 10–8. What is the pH of a solution with an
initial concentration of 0.20 M hypochlorous acid ?
A. 3.41
B. 4.11
C. 6.82
D. 2.89
22
Your Turn! - Solution
[HOCl] [H3O+] [OCl–]
I 0.20 M 0 0
C –x +x +x
E 0.20 – x x x
23
Your Turn!
The Ka for benzoic acid is 6.5 x 10-5. What is the pH
of a 0.10 M benzoic acid solution?
A. 2.60
B. 4.19
C. 2.09
D. 1.59
24
Simplifications in Acid-Base
Equilibrium Calculations
Morphine, C17H19O3N, is administered medically to
relieve pain. It is a naturally occurring base, or
alkaloid.
What is the pH of a 0.075 M solution of morphine at
25 °C?
The base ionization constant, Kb, is 1.6 × 10–6 at 25 °
C.
25
Acid-Base Calculations (cont)
[C17H19O3N] [HC17H19O3N+] [OH–] (M )
(M ) (M )
I 0.075 0 ~0
C –x +x +x
E 0.075 – x x x
26
Acid-Base Calculations (cont)
= 3.5 × 10–4 M
• x ≈ [OH–] = 3.5 × 10–4 M
• Check assumption 3.5 × 10–4 < 0.075
• pOH = –log (3.5 × 10–4) = 3.46
• pH = 14.00 – pOH
• = 14.00 – 3.46 = 10.54
• Notice if c >> Kb,
• Then [base]equilibrium ≈ [base]initial
• Also if c >> Ka
• Then [HA]equilibrium ≈ [HA]initial
27
Your Turn!
Calculate the pH for a solution of 0.025 M pyridine
(py). Kb = 1.7 × 10-9
py + H2O pyH+ + OH–
A. 5.23
B. 8.77
C. 8.81
D. 5.19
28
Equilibrium Calculations when
Simplifications Fail
Weak acid, HA, ionizes in water to give ions
HA(aq) + H2O A–(aq) + H3O+(aq)
[HA]equilibrium = [HA]initial – x
30
The Quadratic Equation
• For a quadratic equation in the form
I 0.15 0 0
C –x +x +x
E 0.15 – x x x 32
• Substituting equilibrium concentrations into equilibrium
law gives:
33
• Or in terms of general quadratic equation
• [H+] = x = 0.065 M
• [C2HCO2Cl2–] = x = 0.065 M
• pH = –log(0.065) = 1.19
35
Next Session
36
Contents
1. Ionization Constant, Ka and Kb
2. Determining Ka and Kb Values
3. pH of Weak Acid and Weak Base Solutions
4. Acid-Base Properties of Salt Solution
5. Buffer Solution
6. Polyprotic Acids
7. Acid-Base Titration
37
Acid-Base Properties of Salt Solution
• Salt is formed by neutralization of an acid by a base.
• HCl + NaOH gives NaCl and H2O
• The pH of salt is not always neutral
• Salts that contain the conjugate acids of weak bases
produce acidic aqueous solution;
• Salts that contain the conjugate bases of weak acids
produce basic aqueous solution.
Note:
• all group 1 and 2 metals (Ex. Li+, Ca2+) and all metal cations
with charge +1 (Ex.Ag+) are neutral.
• Conjugate base from strong acid (HCl, HBr, HI, HClO4, HClO3,
H2SO4, HNO3) is really weak base or almost neutral.
38
How to predict acidic/basic
properties of salts ??
1. Write chemical equation of salt in water
2. Write the equilibrium equation of its cation or anion
Example:
NH4Cl is acid or base?
Answer:
Remember:
+ -
1. NH4Cl (salt) 🡪 NH4 + Cl Cl- + H2O 🡪 no reaction
neutral
• Cl-
40
NH3 is weak base
41
42
• NH4Cl
So overall Acidic 43
Your Turn
• Predict whether the pH is acidic, basic, or neutral
for a solution of NaCH3CO2 ?
Ka of HCH3CO2 = 1.76 x 10-5
Answer:
• NaCH3CO2 🡪 Na+ + CH3CO2−
neutral
• CH3CO2− + H2O ⇌ HCH3CO2 + OH−
Basic
Thus, NaCH3CO2 has basic property.
44
Or you can use another way
• Predict whether the pH is acidic, basic, or neutral
for a solution of NaCH3CO2 ?
Ka of HCH3CO2 = 1.76 x 10-5
Answer:
• Na+ Is Na+ a conjugate acid of a weak base? NO
Neutral
-
-
Is CH 3
CO 2
a conjugate base of a weak acid?
• CH3CO2 Is HCH CO a weak acid? YES YES
3 2
Basic
So overall Basic 45
General Rule for Compound XY
• X+ Is X+ a conjugate acid of weak base?
If yes, then acidic;
If No, neutral
48
Your Turn !
What is the pH of a 1.00 molar solution of NaCN(aq)?
The Ka for HCN = 6.2 × 10‑10.
a. 2.40
b. 4.61
c. 9.40
d. 11.60
e. 13.00
49
Buffers
• A buffer solution is any solution that maintains an
approximately constant pH despite small additions
of acid and base.
• An acid buffer: consists of a weak acid and its
conjugate base supplied as a salt. It buffers on the
acidic side of neutral
• An basic buffer: consists of a weak base and its
conjugate acid supplied as a salt. It buffers on the
basic side of neutral.
50
Acid Buffer Example
• Mix acetic acid with an acetate salt and get dynamic
equilibrium:
• CH3CO2H (aq) + H2O (l) ⇌ H3O+ (aq) + CH3CO2- (aq)
• What happens if strong acid is added to a solution
containing approximately equal amounts of CH3CO2H
and CH3CO2- ?
back reaction
51
Acid Buffer Example
• Mix acetic acid with an acetate salt and get dynamic
equilibrium:
• CH3CO2H (aq) + H2O (l) ⇌ H3O+ (aq) + CH3CO2- (aq)
52
Acid Buffer Action
• The weak acid, HA, transfers protons to OH- ions
supplied by strong base.
• The conjugate base, A-, of the weak acid accepts
protons from the H3O+ ions supplied by a strong
acid.
• A strong acid and the salt of its conjugate base
don’t make a good buffer. Why?
• Strong acids goes to completion
Drives to right
53
Base Buffer Example
• NH3 (aq) + H2O (l) ⇌ NH4+ (aq) + OH- (aq)
54
Base Buffer Action
• The weak base, B, accepts protons supplied by
strong acid.
• The conjugate acid, BH+, of the weak base
transfers protons to the OH- ions supplied by a
strong base
55
How to Calculate pH of
Buffer solutions?
• Important :
1. Write the equilibrium equation on the system
2. Table of ICE (analyze what we have in initial
condition)
3. Get [H3O+] or [OH-] to calculate pH.
56
Learning Check
A buffered solution contains initial concentrations of
0.55 M acetic acid (CH3COOH, Ka = 1.8 × 10–5) and
0.45 M sodium acetate (CH3COONa). Calculate the pH
of this solution.
CH3COOH(aq) ⇌ CH3COO–(aq) + H+(aq)
= 1.8 × 10–5
57
Concentra- [HC2H3O2H] (M ) [C2H3O2–] (M ) [H+] (M )
tion (M)
Starting 0.55 0.45 0
Change –x +x +x
Equilibrium 0.55 – x ≈ 0.55 0.45+x ≈ 0.45 x
58
• Solving for x gives
A. 10.18
B. 6.60
C. 3.82
D. 4.58
60
Learning Check
A student has available 1.00 L of the buffered
solution: 0.55 M acetic acid (CH3COOH, Ka = 1.8 ×
10–5) and 0.45 M sodium acetate (NaCH3COO).
What is the pH of this buffer after 0.060 mol of
OH– are added to the reaction?
Answer:
Step 1. Calculate pH of buffer
•Before OH– is added the pH of the buffer is 4.66 or
• [H+] = 2.2 × 10–5 M
61
Learning Check (Cont.)
Step 2: Calculate moles of HA and A– from reaction
CH3COOH(aq) + OH–(aq) CH3COO–(aq) + H2O(aq)
• Rearrange:
• Take logarithms of both sides:
65
• HA (aq) + H2O (l) ⇌ H3O+ (aq) + A- (aq)
rearrange
Equilibrium concentration
66
• The values of [HA] and [A-] in the equation are at
equilibrium.
67
Equilibrium concentration
Initial concentration
Handerson-Hasselbalch Equation
Note: This assumption is valid when [H3O+] is small compared to [HA] and [A-]
(i.e. less than 5% or initial conc. ≧ 400 Ka) 68
Example: Design a buffer
system with pH 4.60
• A buffer solution is most effective in the
range of pKa ± 1
Acid HA
Benzoic 4.19
Oxalic 4.19
Hydrazoic 4.72
Acetic 4.75
Propionic 4.87
Pyridinium Ion 5.25
71
Your Turn! - Solution
72
Calculate pH of Buffer
(Homework)
Calculate the pH of a buffer solution that is 0.040 M
NH4Cl(aq) and 0.030 M NH3(aq).
Step 1: Equilibrium:
NH4+(aq) + H2O(l ) NH3(aq) + H3O+(aq)
73
• Step 2: Calculate pH
or
74
For bases use Kb and equilibria to calculate [OH–], pOH,
and finally pH
NH3(aq) + H2O NH4+(aq) + OH–(aq)
75
Calculate pOH
pOH = –log(1.35 × 10–5) = 4.87
Calculate pH
pH = 14.00 − 4.87 = 9.13
76
Calculate pH of Buffer (Homework)
Can 1.00 L of this buffer system deal with the addition
of 0.010 mol of H+? What is the final pH in this case?
NH3(aq) + H2O NH4+(aq) + OH–(aq)
79
Polyprotic Acids
• Some inorganic polyprotic acids:
• Phosphoric acid H3PO4
• Carbonic acid H2CO3
• Sulfuric acid H2SO4
• Sulfurous acid H2SO3
• These acids undergo ionization in steps
• H3PO4(aq) + H2O H3O+(aq) + H2PO4–(aq)
• H2PO4–(aq) + H2O H3O+(aq) + HPO42–(aq)
• HPO42–(aq) + H2O H3O+(aq) + PO43–(aq)
80
Polyprotic Acids
• Or in simpler terms
H3PO4(aq) H+(aq) + H2PO4–(aq)
81
Next Session
82
Contents
1. Ionization Constant, Ka and Kb
2. Determining Ka and Kb Values
3. pH of Weak Acid and Weak Base Solutions
4. Acid-Base Properties of Salt Solution
5. Buffer Solution
6. Polyprotic Acids
7. Acid-Base Titration
83
Acid Base Titration
• An acid base titration is the addition of a volume of
base of known concentration to acid of unknown
concentration (or addition of acid to base).
84
Titration Curve
Equivalence point or
stoichiometric point
or end point
Equivalence (stoichiometric, s) point:
the theoretical volume at which the amount
of base added equals the amount of acid that
was originally present
End point:
the experimentally measured volume at which
the indicator changes color.
85
Titration Curve
Equivalence point or
stoichiometric point
or end point
Before At After
Endpoint Endpoint Endpoint
buret
titrant
analyte
86
Figures by MIT OpenCourseWare
Titration Curve
• Initial pH is low
88
Titration Curve of Strong Acid with
Strong Base
Steep
89
H+(aq) + OH–(aq) → H2O(aq)
2. During titration: before equivalence
• 50.00 mL of 0.100 M HCl
• 10.00 mL of 0.200 M NaOH added
H+(aq) mmol OH–(aq) mmol
Before 50.0 mL × 0.100 M = 10.0 mL × 0.200 M =
5.00 mmol 2.00 mmol
Rxn –2.00 mmol –2.00 mmol
After = 3.00 mmol = 0.00 mmol
pH = – log(0.0500) = 1.30 90
3. At Equivalence Point
• 50.00 mL of 0.100 M HCl
• 25.00 mL of 0.200 M NaOH added
H+(aq) + OH–(aq) → H2O(aq)
H+(aq) mmol OH–(aq) mmol
Before 50.0 mL × 0.100 M 25.0 mL × 0.200 M
= 5.00 mmol = 5.00 mmol
Rxn –5.00 mmol –5.00 mmol
After = 0.00 mmol = 0.00 mmol
• What is pH?
• Na+ has no acid or base properties
• Cl– is anion of strong acid, so very weak base
• Neither Na+ nor Cl– affect pH
• So solution is neutral
• pH = 7.00
• True for equivalence point of all strong acids reacting
with strong bases
92
4. After equivalence point
• 50.00 mL of 0.100 M HCl
• 50.00 mL of 0.200 M NaOH added (Now OH– is in
excess)
H+(aq) + OH–(aq) → H2O(aq)
V=Veq A- A- A- A-
H H
V=V half eq
A A A- A-
H H H
0<V<Veq A A A A-
H H H H
V=0
A A A A
95
Titration of Weak Base
with Strong Acid
96
Titration: Weak Acid with Strong
Base
A 25.00 mL sample of 0.200 M acetic acid (CH3COOH) is
titrated with 0.200 M NaOH.
98
2. During titration: before equivalence (buffer problem)
• 25.00 mL of 0.200 M acetic acid
• 10 mL of 0.200 M NaOH added
OH– + CH3COOH → CH3COO– + H2O
100
2b. During titration: halfway to equivalence
• 25.00 mL of 0.200 M acetic acid
• 12.5 mL of 0.200 M NaOH added
101
2b. During titration: halfway to equivalence
• 25.00 mL of 0.200 M acetic acid
• 12.5 mL of 0.200 M NaOH added
102
3. At equivalence point—Stoichiometry
• 25.00 mL of 0.200 M acetic acid
• 25.00 mL of 0.200 M NaOH added
•
OH– + CH3COOH → CH3COO– + H2O
103
3. At equivalence point—Dilution Factor
• 25.00 mL of 0.200 M acetic acid
• 25 mL of 0.200 M NaOH added
104
3. At the equivalence point—Weak Base
CH3COO– + H2O CH3COOH + OH–
105
3. At the equivalence point
CH3COO– + H2O CH3COOH + OH–
106
4. After equivalence point—Stoichiometry
107
4. After equivalence point—Excess Base
• 25 mL of 0.200 M CH3COOH
• 35 mL of 0.200 M NaOH
108
Your Turn!
What is the change in pH when 10.0 mL of 0.100 M
NaOH is added to 50.0 mL of 0.250 M acetic acid?
The acid ionization constant for acetic acid is 1.8 ×
10–5. The initial pH of the acetic acid is 2.67.
A. –1.01
B. 3.13
C. 1.01
D. –3.13
109
Your Turn! - Solution
• First, determine the initial mmoles of acid and base:
111
Your Turn!
A 10.0 mL solution of 0.300 M NH3 is titrated with
0.100 M HCl. Calculate the pH after the addition of
10.0 mL of acid.
A. 9.55
B. 9.25
C. 8.95
D. 9.73
E. 8.77
112
Your Turn! - Solution
• First, determine the initial mmoles of acid and base:
114
Homework
• The titration of 25.00 mL of 0.100 M CH3CO2H with
0.100 M NaOH. Ka = 1.8 × 10−5 for CH3CO2H.
115