Lecture 14

Acid-base

Huynh Kim Lam Chemistry for Engineers (CH011IU) | Lecture 14 | Semester 1: 2022-2023
1 huynhkimlam.iu@gmail.com / lamhuynh.info
General Properties of Aqueous Solutions

 A solution: a homogenous mixture of ≥ 02 substances

• The solute: the substance present in a smaller amount
• The solvent: the substance present in a larger amount
Ex: a mixture of 60% ethanol & 40% water  solvent? solute?

 Aqueous Solutions
• The solute initially is a liquid or a solid
• The solvent is water

2 Solute: chất tan; solvent: dung môi; aqueous solution: dung dịch nước
Electrolytes

An electrolyte is a substance that dissolves in water to give

an electrically conducting solution
• Generally, ionic solids that dissolve in water are electrolytes
Ex: NaCl, KBr
• Strong electrolyte is an electrolyte that exits in solution almost
entirely as ions
Ex: NaCl → Na+(aq) + Cl-(aq) (100%)
• Weak electrolyte is an electrolyte that dissolves in water to give a
relatively small percentage of ions
Ex: NH3(aq) + H2O(l) ↔ NH4+(aq) + OH-(aq) (~3%)

A nonelectrolyte is a substance that dissolves in water to give

a non-conducting or very poorly-conducting solution
• Generally, molecular substances are nonelectrolyte
Ex: sucrose - C12H22O11, methanol

3 Electrolyte: chất điện giải

 Electrolytes vs. Nonelectrolytes

nonelectrolyte weak electrolyte strong electrolyte

Ex: pure water Ex: NaCl/H2O

A solution’s ability to conduct electricity

depends on the number of ions it contains
Note that the same amounts of the dissolved solutes are used in the 03 cases

Copyright © 2007 by The McGraw-Hill Companies, Inc

4
 Electrolytes
A “strong” electrolyte is completely dissociated
A “weak” electrolyte is partially dissociated
A nonelectrolyte is not dissociated

Copyright © 2011 by The McGraw-Hill Companies, Inc.

Strong electrolyte
𝐻𝐶𝑙 𝑎𝑞 → 𝐻 𝑎𝑞 𝐶𝑙 𝑎𝑞
Weak electrolyte
𝐶𝐻 𝐶𝑂𝑂𝐻 𝑎𝑞 ↔ 𝐶𝐻 𝐶𝑂𝑂 𝑎𝑞 𝐻 𝑎𝑞
5 Nonelectrolyte: 𝐶𝐻 𝑂𝐻 𝐻 𝑂 → 𝐶𝐻 𝑂𝐻(aq)
Hydration

The process in which an ion is surrounded by water

molecules arranged in a specific manner is called hydration.

Hydration of Na+ and Cl- ions

Copyright © 2011 by The McGraw-Hill Companies, Inc.

Hydration helps to stabilize ions in solution and prevents cations from combining
with anions.

6 Hydration: hydrate hóa

Review

Copyright © 2011 by The McGraw-Hill Companies, Inc.

7
Review: Important Reactions in Solution

 Precipitation Reactions

 Acid-base Reactions

 Oxidation-Reduction Reactions

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Acid–Base Reactions: Facts

 Basis of many medicinal and household products

• Aspirin: acetyl salicylic acid
• Milk of magnesia: magnesium hydroxide

 Important in industrial processes

 Essential in sustaining biological systems

9
General Properties of Acids and Bases

Acids
• Have a sour taste (e.g., vinegar – acetic acid, lemon juice – citric
acid)
• Cause color changes in plant dyes (litmus paper: blue => red)
• React with certain metals (e.g., Zn, Mg, …) to produce hydrogen
gas (H2)
• React with carbonates and bicarbonates (CO32-, HCO3-) to
produce CO2
• Aqueous acid solutions conduct electricity

Bases
• Have a bitter taste
• Feel slippery (e.g., soap)
• Cause color changes in plant dye (litmus paper: red => blue)
• Aqueous base solution conduct electricity

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Acid–Base Reactions

Acid + base  salt + water

Acid? Base?

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Arrhenius Theory (Nobel Prize 1894)

An acid produces hydrogen ions, H+ (or H3O+), when it dissolves

in water.

HX(aq) → H+(aq) + X-(aq) (or HX + H2O → H3O+(aq) + X-(aq))

Ex: HNO3(aq) → H+(aq) + NO3-(aq)

A base produces hydroxyl ions (OH-), when it dissolves in water.

MOH(aq) → M+(aq) + OH-(aq)

Ex: NaOH(s) → Na+(aq) + OH-(aq)

Limitation: Apply only to aqueous solutions & some cases

cannot define acid/base
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Example

HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l)

Ionic equation:
H+(aq) + Cl-(aq) + Na+(aq) + OH-(aq) → Na+(aq) + Cl-(aq) + H2O(l)

Net ionic equation:

H+(aq) + OH-(aq) → H2O(l)

Acid: HCl
Base: NaOH

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 Question

NH3(aq) + H2O(l) ↔ NH4+(aq) + OH-(aq)

Acid ? Base?

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 Bronsted-Lowry Theory

Johannes N. Bronsted and Thomas M. Lowry ’s view:

acid-base reactions are proton-transfer reactions

NH3(aq) + H2O(l) ↔ NH4+(aq) + OH-(aq)

 Acids: the species (molecule or ion) that donates a

proton to another species in a proton-transfer reaction
(≡ proton donor)

 Bases: the species (molecule or ion) that accepts a

proton in a proton-transfer reaction (≡ proton acceptor)

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 Bronsted-Lowry Theory

Acid: CH3COOH
Base: NaOH

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Bronsted-Lowry Theory
Conjugate Acids and Bases

 When an acid donates a proton in an acid-base

reaction, it forms a conjugate base.
 When a base accepts a proton in an acid-base reaction,
it forms a conjugate acid.

17 Conjugate: liên hợp

Bronsted-Lowry Theory – Amphiprotic

HA + H2O ↔ A- + H3O+
acid1 base2 conj. base1 conj. acid2

 acid1 ↔ conj. base1 + proton

 base2 + proton ↔ conj. acid2

 Water can act as an acid or a base.

“Amphiprotic” solvents can be either acids or
bases

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Bronsted-Lowry Theory - Amphiprotic

Other amphiprotic solvents:

 methanol (CH3OH)
 ethanol (CH3CH2OH)
 glacial acetic acid (CH3COOH)

Some amphiprotic solutes:

 HCO3- + H2O ↔ H3O+ + CO32-
 HCO3- + H2O ↔ H2CO3 + OH-
 HPO42- + H2O ↔ H3O+ + PO43-
 HPO42- + H2O ↔ H2PO4- + OH-

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Bronsted-Lowry Theory
Bronsted-Lowry Theory - Strength

The stronger the conjugate acid is,

the weaker the conjugate base is and vice versa

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Lewis Theory

Lewis acid - a substance that accepts an electron pair

Lewis base - a substance that donates an electron pair

Example: formation of hydronium ion

base acid

 Electron pair of the new O-H bond originates on the Lewis

base
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Lewis acid-base reaction

22
Summary

Acids
• Arrhenius : H+ donor in aqueous solution
• Bronsted-Lowry : H+ donor in aqueous solution
• Lewis : e- pair acceptor

Bases
• Arrhenius : OH- donor in aqueous solution
• Bronsted-Lowry : H+ acceptor in aqueous solution
• Lewis : e- pair donor

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Acid-base strength

The strength of an acid (or base) is determined by the

amount of ionization (reflected by ionization constant, K)

H3O(aq)
+
 Cl-(aq) 
eq eq
Kionization  Ka  ?
HCl(aq) 
eq

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Acid-base strength

A strong acid is an acid that ionizes completely in water;

it is a strong electrolyte

A weak acid is an acid that only partly ionizes in water; it

is a weak electrolyte

A strong base is a base that present in aqueous

solution entirely as ions, one of which is OH-; it is a
strong electrolyte

A weak base is a base that is only partly ionized in

water; it is a weak electrolyte

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Strong acids
Copyright © 2007 by The McGraw-Hill Companies, Inc

26
Weak acids
Copyright © 2007 by The McGraw-Hill Companies, Inc

27
Common strong acids and bases

28
Relative Strengths of Acids and Bases

29
Effect of atom Y on the acid strengths of acids H-O-Y

The acidity increases with the electronegativity of Y.

Which one is a stronger acid?

H-O-Cl is more acidic than H-O-Br.

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Water: autoprotolysis

Autoprotolysis: amphiprotic solvents undergo self-ionization

Water can act as an acid and a base

- When it reacts with an acid, it is a base
- When it reacts with an base, it is an acid

 Autoprotolysis refers to water acting as both an acid and a

base to react with itself

H2O + H2O ↔ H3O+ + OH-

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Water: Ionization

The ionization constant Kw for water.

The actual reaction is the proton transfer:

2H2O ↔ H3O+ + OH-

 Kw = [H3O+] [OH-]

 This special equilibrium constant is referred to as the

ionization constant for water, Kw.

 At 25°C, Kw = 1.0  10−14

32
Relation of [H+],[OH-] and pH

pH is defined as the negative base-10 logarithm of the

hydronium ion concentration.
pH = −log [H3O+]
• In pure water,
Kw = [H3O+] [OH−] = 1.0  10−14

– Because [H3O+] = [OH−]

 [H3O+] = (1.0  10−14)1/2 = 1.0  10−7
pH = −log (1.0  10−7) = 7.00

– An acid has a higher [H3O+] than pure water, so its pH is <7

– A base has a lower [H3O+] than pure water, so its pH is >7.

33
Relation of [H+],[OH-] and pH
Copyright © 2007 by The McGraw-Hill Companies, Inc

34
Ion concentration (mol/L)
Copyright © 2007 by The McGraw-Hill Companies, Inc

35
pH values

36
pH measurement
For less accurate measurements, one can use
– Litmus paper
• “Red” paper turns blue above ~pH = 8
• “Blue” paper turns red below ~pH = 5
– An indicator

37
pH measurement

For more accurate

measurements, one
uses a pH meter, which
measures the voltage in
the solution.

38
Equilibrium Constants for Weak Acids

Consider acetic acid, CH3COOH

CH3COOH ↔ H+ + CH3COO-
CH3COOH + H2O ↔ H3O+ + CH3COO-
Acid Conj. base

𝑯𝟑 𝑶 𝑪𝑯𝟑 𝑪𝑶𝑶 𝟓
𝑲𝒂 𝟏. 𝟖 𝟏𝟎
𝑪𝑯𝟑 𝑪𝑶𝑶𝑯

 Ka ≡ Keq for ACID (ionization, dissociation)

 Ka gives the ratio of ions (split up) to molecules (don’t split
up)

39
Equilibrium constants for weak acids

 Weak acid has Ka < 1

 Leads to small [H3O+] and a pH of 2 - 7

40
Equilibrium constants for weak acids

The greater the value of Ka, the stronger the acid.

Huynh Kim Lam Chemistry for Engineers (CH011IU) | Lecture 14 | Semester 1: 2022-2023
41 huynhkimlam.iu@gmail.com / lamhuynh.info
Equilibrium Constants for Weak Bases

 Weak base has Kb < 1

 Leads to small [OH-] and a pH of 12 - 7

42
Ka & Kb Relationship

HCN(aq) + H2O(l) ↔ CN-(aq) + H3O+(aq) 𝐾 𝐻𝐶𝑁

Acid Conj. base

CN-(aq) + H2O(l) ↔ HCN(aq) + OH-(aq)

Base Conj. acid

2H2O(l) ↔ H3O+(aq) + OH-(aq) 𝐾 𝐻 𝑂 𝑂𝐻

Ka Kb = Kw=10-14

43
Ionization constants for acids/bases

Acids Conjugate
Bases
Increase
strength

Increase
strength

44
Ka, Kb, [H3O+] and pH relation

45
pH calculation from Ka

Calculate the pH of a 0.300M solution of acetic acid,

HC2H3O2, at 25°C.
HC2H3O2(aq) + H2O(l) ↔ H3O+(aq) + C2H3O2−(aq)
Given: Ka for acetic acid at 25°C is 1.8  10−5.

𝟑 𝟐 𝟑 𝟐
𝐚

pH = −log [H3O+]

= 2.64

46
pH calculation from Kb
What is the pH of a 0.15 M solution of NH3?
NH3(aq) + H2O(l) ↔ NH4+(aq) + OH-(aq)
Given: Kb for ammonia solution is 1.8x10-5

b =1.8x10-5

 [OH−] = 1.6  10−3 M

 pH = 11.20

47
pH of a Salt Solution

What is the pH value of 0.1M NaCN(aq)?

Given: Ka for HCN is 4.9x10-10

48
Buffer
A mixture of a weak acid and its conjugate base
(OR a mixture of a weak base and its conjugate acid)

Function: resist change in pH

 when acids or bases are added or
 when dilution occurs.

Mix:
X moles of weak acid (HA) + Y moles of conjugate base (A-)
HA ↔ H+ + A-
Found:
• moles of acid HA remains ~X
• moles of base A- remains ~Y
 Very little reaction shift
49
Buffers
HA ↔ H+ + A-

Addition of H+:
H+ reacts to completion with the strong conjugate base (A-)
present

H+ + A-  HA or H+ + B  BH+

Addition of OH-:
OH- reacts to completion with the weak acid (HA) present

OH- + HA  H2O + A- or OH- + BH+  H2O + B

[H+] essentially unchanged  pH unchanged

50
Buffers

Strong base neutralizes weak acid Strong acid neutralizes weak base

51
pH of a buffer

A 2-ingredient problem
0.10M CH3COOH + 0.20M CH3COO-
pH = 5.05

52
Henderson-Hasselbalch equation

For acids (HA): HA  H+ + A-

• When [A-] = [HA]  pH = pKa

For bases (B): B + H+  BH+

• pKa applies for the acid BH+ = B + H+

𝐾

53
10% acetate
Buffers ion 90% acetic acid
10% acetate ion & 90% acetic acid

.
pH
.

pH = 4.76 + (-0.95)

= 3.81

54
50% acetate
Buffers ion 50% acetic acid
50% acetate ion & 50% acetic acid

.
pH
.

pH = 4.76 + (0)

= 4.76 (= pKa)

55
Buffers

90% acetate ion & 10% acetic acid

.
pH
.

pH = 4.76 + (0.95)

= 5.71

56
Buffer capacity

• refers to the ability of the buffer to retard changes in pH when

small amounts of acid or base are added

• the ratio of [A-]/[HA] determines the pH of the buffer

• the magnitude of [A-] & [HA] determine the buffer capacity

• Buffer capacity: number of moles of a strong base needed

to raise the pH of 1 L of buffer by 1 pH unit.

[ A ]
pH  pK A  log
[ HA0 ]

57
Effect of [A-]/[HA] on pH

58
Buffer capacity
[ A ]
pH  pK A  log
[ HA0 ]
- 0 - 0
[A ]/[HA ] pH ([A ]/[HA ])’ pH’ pH = pH’ - pH
1/99 3.00 2/98 3.31 0.31
10/90 4.05 11/89 4.09 0.04
20/80 4.40 21/79 4.42 0.02
50/50 5.00 49/51 4.98 -0.02
80/20 5.60 79/21 5.58 -0.02
90/10 5.95 89/11 5.91 -0.04
99/1 7.00 98/2 6.69 -0.31
99.9/0.1 8.00 98.9/1.1 6.95 -1.05

59
Buffer capacity

A buffer is most effective in resisting

changes in pH when:
pH = pKa
i.e.: [HA] = [A-]

 Choose buffer whose pKa is as

close as possible to the desired pH.
pKa  1 pH unit

60
Problem

Calculate the pH of a solution containing 0.200 M NH3 and

0.300 M NH4Cl
Given: acid dissociation constant for NH4+ is 5.7x10-10.

NH3 + H2O ↔ NH4+ + OH-

Base Acid

pH = 9.07

61
Problem

Calculate the volume of 0.200 M NH3 and 0.300 M NH4Cl to

make a buffer solution having pH = 10.0
Given: acid dissociation constant for NH4+ is 5.7x10-10.

NH3 + H2O ↔ NH4+ + OH-

Base Acid

62
Structures and pKa values

63
Structures and pKa values

64
Structures and pKa values

65
Structures and pKa values

66
Titration
Titration: one solution of known concentration is used to
determine the concentration of another solution through a
monitored reaction.

The equivalence point in the titration occurs when all the moles of
H+ ions present in the original volume of acid solution have
reacted with an equivalent number of moles of OH- ions added
from the burette.

Copyright © 2007 by The McGraw-Hill Companies, Inc

67
Essential Terms/Concepts/Equations

Electrolyte Chất điện ly

Buffer (solution) Dung dịch đệm
Solute Chất tan
Solvent Dung môi
Aqueous solution Dung dịch với dung môi là nước
Hydration Quá trình hydrate hóa
Conjugate acid/base Acid/base liên hợp
Amphiprotic solvent Dung môi lưỡng tính (có thể đóng vai trò là acid và base)
Autoprotolysis Quá trình tự ion hóa của dung môi lưỡng tính
:
Equilibrium constant Hằng số cân bằng
Buffer capacity Khả năng chống thay đổi pH của dung dịch đệm

68
End of lecture 14

Thank you!

69
Ion concentration (mol/L)

pH Hydrogen Ion (H+) Hydroxyl Ion (OH-)

Acid 0 1 0.00000000000001
1 0.1 0.0000000000001
2 0.01 0.000000000001
3 0.001 0.00000000001
4 0.0001 0.0000000001
5 0.00001 0.000000001
6 0.000001 0.00000001
Neutral 7 0.0000001 0.0000001
8 0.00000001 0.000001
9 0.000000001 0.00001
10 0.0000000001 0.0001
11 0.00000000001 0.001
12 0.000000000001 0.01
13 0.0000000000001 0.1
Alkaline 14 0.00000000000001 1

Huynh Kim Lam Chemistry for Engineers (CH011IU) | Lecture 14 | Semester 1: 2022-2023
70 huynhkimlam.iu@gmail.com / lamhuynh.info
Examples

Huynh Kim Lam Chemistry for Engineers (CH011IU) | Lecture 14 | Semester 1: 2022-2023
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Titration
Titration of a strong acid with strong base at various
concentrations of acid and base.

Huynh Kim Lam Chemistry for Engineers (CH011IU) | Lecture 14 | Semester 1: 2022-2023
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Titration
Titration of a strong base with strong acid.

Huynh Kim Lam Chemistry for Engineers (CH011IU) | Lecture 14 | Semester 1: 2022-2023
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Titration
Titration of weak acids with strong base.

Huynh Kim Lam Chemistry for Engineers (CH011IU) | Lecture 14 | Semester 1: 2022-2023
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Titration
Buffer regions in titration curves.

Huynh Kim Lam Chemistry for Engineers (CH011IU) | Lecture 14 | Semester 1: 2022-2023
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Titration

Titration of a weak acid with strong base in presence of indicators.

Huynh Kim Lam Chemistry for Engineers (CH011IU) | Lecture 14 | Semester 1: 2022-2023
76 huynhkimlam.iu@gmail.com / lamhuynh.info
Titration

Titration of a weak base with strong acid.

Huynh Kim Lam Chemistry for Engineers (CH011IU) | Lecture 14 | Semester 1: 2022-2023
77 huynhkimlam.iu@gmail.com / lamhuynh.info