UNIVERSITY OF SCIENCE-VNUHCM

FACULTY OF CHEMISTRY

Chapter 5.
Acid-Base Equilibrium
 Contents
5.1. Acids, Bases, and Conjugate Acid–Base Pairs
5.2. Ionization of Acids and Bases in Water
5.3. Self-Ionization of Water and the pH Scale
5.4. Strong Acids and Strong Bases
5.5. Weak Acids and Weak Bases
5.6. Polyprotic Acids
5.7. Hydrolysis; Ions as Acids and Bases
5.8. Qualitative Aspects of Acid–Base Reactions
5.9. Molecular Structure and Acid–Base Behavior
5.10. Lewis Acids and Bases
5.11. The Common-Ion Effect in Acid-Base Equilibria
5.12. Buffer Solutions
5.13. Acid-Base Indicators
5.14. Neutralization Reactions and Titration Curves
5.15. Solutions of Salts of Polyprotic Acids
5.1. Acids, Bases, and Conjugate Acid–Base Pairs

❑ Arrhenius theory:
– Acid: Substance that, when dissolved in water,
increases the concentration of hydrogen ions.
–Base: Substance that, when dissolved in water,
increases the concentration of hydroxide ions.
 The Arrhenius Theory
❑ Substance dissociates in solution to yield ν ions consisting of ν+ cations
and ν- anions (ν is electrolytic order)
CH3COOH ⇄ CH3COO− + H+
HCl = H+ + Cl-

❑ The degree of dissociation is the equilibrium degree of conversion,

the fraction of the number of molecules originally present that
dissociated at the given concentration.
n'
=
n
❑ Electrolytic dissociation is reversible reaction, that equilibrium
state is described by the law of mass action.
n n-
[M + ] + .[A- ]
𝑀𝜈+ 𝐴𝜈 − ⇄ 𝜈+ 𝑀+ + 𝜈− 𝐴− K dis =
[Mn An- ]
+ 4
Solvation

The dissociation of NaCl crystals in water

5
HYDRONIUM ION (H3O+)

6
❑ Brønsted–Lowry

– Acid: Proton donor: must have a removable (acidic)

proton.
– Base: Proton acceptor: must have a pair of nonbonding
electrons.
❑ Conjugate Acid–Base Pairs
❑ Conjugate Acids and Bases
• Reactions between acids and bases always
yield their conjugate bases and acids.
5.2. Ionization of Acids and Bases in Water
❑ Acid Ionization constant
Kc
CH3CO2H(aq) + H2O(l) H3O+(aq) + CH3CO2−(aq)

[H + ][A - ] Ca .Ca  2Ca

Ka = = =   2Ca
[HA] (1 −  )Ca 1 − 
Ka
+
[H ] = [A ] =
-
K a .Ca =
Ca
❑ Base Ionization Constant

Kc
NH3 + H2O ⇄ NH4+ + OH-

Kb
- -
[OH ] = [NH ] = K b .Cb
4 a=
Cb
❑ Ionization constants of weak acids, bases
5.2. The Self-Ionization of Water, the pH Scale

1000 g / l
[H 2 O] = C H 2O = = 55,5(5)mol / l
18 g / mol

ToC 0 10 18 25 50
Kw.1014 0,114 0,292 0,570 1,008 5,474
❑ The pH Scale

➢ pH = −log [H3O+]

➢ pOH = -log[OH-]

▪ For pure water: pH = −log (1.0  10−7) = 7.00

▪ Kw=[H+][OH-] =10-14 ➔ -logKw=-log[H+]-log[OH-]

▪ pKw=pH +pOH =14

❑ Acidic, Basic, and Neutral Solutions

These are the

pH values for
several
common
substances.
❑ pH Chart

16
❑ pH meter
❖ For more accurate measurements, one uses a pH meter,
which measures the voltage in the solution.
 5.4. Strong acids and bases
❑ Strong acids and bases are strong
The Common strong acids and bases
electrolytes and exist totally as ions in
aqueous solution Acid Base
❑ A strong acid or base has a large HCl LiOH
ionization constant: Ka or Kb is much
greater than 1. HBr NaOH
HI KOH
HClO4 RbOH
HNO3 CsOH
H2SO4 Mg(OH)2
Ca(OH)2
Sr(OH)2
Ba(OH)2
H2SO4 ionizes in two distinct steps. It is
a strong acid only in its first ionization
Calculating Ion Concentrations in an Aqueous Solution of
a Strong Acid
Calculating the pH of an Aqueous Solution of a Strong Base
 How do we calculate in an extremely dilute solution of a
strong acid?
EX.3. Calculating the pH of a solution as dilute as 1.0 x10-8 M HCl
 5.5. Weak acids and bases
❑ Weak acid or base, the corresponding ionization reaction occurs to a
limited extent, with a significant fraction of the acid or base not ionized
❑ A weak acid or base has a small ionization constant: Ka or Kb is much
less than 1

Lactic acid, CH3CH(OH)COOH Glycine, NH2CH2COOH Pyridine, C5H5N

❑ Ionization constants of weak acids, bases
5.3. Weak acids and bases

❖ Strong acids are completely

dissociated in water.

– Their conjugate bases are quite

weak.

❖ Weak acids only dissociate partially

in water.

– Their conjugate bases are weak

bases.
 Example 1. Calculating Ka from the pH

• The pH of a 0.10 M solution of formic acid,

HCOOH, at 25°C is 2.38. Calculate Ka for formic
acid at this temperature.
Solve:

HCOOH + H2O ⇄ HCOO- + H3O+

[H3O+] [HCOO−]
Ka =
[HCOOH]
 Calculating Ka from the pH
pH = −log [H3O+] = 2.38
10−2.38 = 10log [H3O+] → [H3O+] = 4.2  10−3 = [HCOO−]

[HCOOH], M [H3O+], M [HCOO−], M

Initially 0.10 0 0

Change −4.2  10-3 +4.2  10-3 +4.2  10−3

At 0.10 − 4.2  10−3 4.2  10−3 4.2  10−3

Equilibrium = 0.0958 = 0.10
[4.2  10−3] [4.2  10−3]
Ka = = 1.8  10−4
[0.10]
 Calculating Ka from the pH

HCOOH + H2O ⇄ HCOO- + H3O+

𝐻3 𝑂+ [𝐻𝐶𝑂𝑂− ] [𝐻3 𝑂+ ]2
Ka= = [H3O+]=[HCOO-]
[𝐻𝐶𝑂𝑂𝐻] [𝐻𝐶𝑂𝑂𝐻]
[HCOOH]=Ca- [H3O+]
[𝐻3 𝑂+ ]= 𝐾𝑎 × 𝐶𝑎

−𝑙𝑜𝑔[𝐻3 𝑂+ ]= −log( 𝐾𝑎 × 𝐶𝑎 )
𝑝𝐻= 1/2(p𝐾𝑎 − 𝑙𝑜𝑔𝐶𝑎 )

p𝐾𝑎=2 𝑝𝐻 + 𝑙𝑜𝑔𝐶𝑎 =2 x 2.38 + log0.10=3.76

Ka = 10-3.76 =1.7 x10-4
Determining a Value of Ka from the pH of a Solution of
a Weak Acid
Calculating the pH of a Weak Acid Solution
Calculating the pH of a Solution of a Weak Base
How do we calculate the pH of a very dilute solution of a very weak acid?
 For 1.0 x10-5 M HCN, we would substitute Ka =6.2x10-10

➢ We begin by assuming that c-x  c and then solving the resulting

expression for x.

 x = 4.87x 10-8 M

➢ We can improve this result by substituting this value of x into the right side
of the equation above and solving again for x. We obtain x = 4.85 x10-8 M.
➢ By substituting this value for x into the equations for x+ y and y, we obtain
x+y =1.27 x10-7 and y = 7.86 x10-8

We calculate pH = log(1.3 x 10-7) = 6.89

❑ Percent Ionization
HA(aq) + H2O(l) H3O+(aq) + A-(aq)

[A-]eq = [H+]eq =  [HA]ini = .Ca

[HA]eq = (1−  ).Ca
[H + ][A - ] Ca .Ca  2Ca
Ka = = =   2Ca
[HA] (1 −  )Ca 1 − 
Ka
= ;  = K.V
+
[H ] = [A ] =
-
K a .Ca
Ca
𝑝𝐻= 1/2(p𝐾𝑎 − 𝑙𝑜𝑔𝐶𝑎 )
❑ Percent Ionization

Degree of ionization in a 1 M solution as a function of acid or base strength

❑ Percent Ionization

Degree of ionization as a function of concentration for acids of varying strength

Calculating Percent Ionization in an Aqueous Solution of an Acid
EX. Calculating Percent Ionization in an Aqueous Solution of an Acid
Determining Percent Ionization as a Function of
Initial Concentration
 5.6. Polyprotic Acids
❑ Phosphoric acid: triprotic acid
H3PO4 + H2O ⇄ H2PO4- + H3O+ Ka1 = 7,1x10-3
H2PO4- + H2O ⇄ HPO42- + H3O+ Ka2 = 6,3x10-8
HPO42- + H2O ⇄ PO43- + H3O+ Ka3 = 4,2x10-12


❑ Ionization Constant of some polyprotic Acid
Calculating Ion Concentrations in a Polyprotic Acid
Solution
Calculating Ion Concentrations in Sulfuric Acid Solutions: Strong
Acid Ionization Followed by Weak Acid Ionization
General Approach to solution equilibrium
calculations
Set up the calculation of the pH of 0.1 M H3PO4
5.7. Hydrolysis
❑ Ion as Acids and Bases
⇄

-14
10 -10
-5
= 5, 6.10
1,8.10
 Relationship Ka and Kb

Base + H2O ⇄ conjugate acids + OH-

Conjugate acids ⇄ Base + H+
[𝐶𝑜𝑛𝑗𝐴𝑐𝑖𝑑][OH − ] [𝐶𝑜𝑛𝑗𝐴𝑐𝑖𝑑][OH − ][𝐻+ ]
𝐾𝑏 = =
[B𝑎𝑠𝑒] [B𝑎𝑠𝑒][𝐻 + ]

[B𝑎𝑠𝑒][𝐻+ ]
𝐾𝑎 =
[𝐶𝑜𝑛𝑗𝐴𝑐𝑖𝑑]

Kw = Kax Kb pKa + pKb = pKw

➢ Ka is large → Kb is small.

Acid is strong → conjugate base is weak

48
 Making Qualitative Predictions About Hydrolysis Reactions

Predict whether each of the following solutions is acidic, basic, or pH neutral:

(a) NaOCl(aq); (b) KCl(aq); (c) NH4NO3 (aq)

49
 Calculating the pH of a Solution in Which Hydrolysis Occurs
Are NaCN(aq) solutions normally acidic, basic, or pH neutral? What is the pH of
0.50 M NaCN(aq).
 Qualitative Aspects of Acid–Base
Reactions
❑ For an acid–base reaction, equilibrium favors the formation of
the weaker acid and the weaker base

❑ If the acid or base in an acid–base reaction is strong, they

react essentially to completion
5.8. Molecular Structure and Acid – Base
Behavior
❑ Strengths of Binary Acid

x106 > > 6,6x10-4

HF + H2O → [F−…..H3O+]  F − + H3O+

❑ Strengths of Binary Acid

❑ The values for NH3 and CH4 are very

small. These molecules do not behave as
acids in water.
❑ When comparing binary acids of elements
in the same row of the periodic table, acid
strength increases as the polarity of the
bond increases.
❑ When comparing binary acids of elements
in the same group of the periodic table,
acid strength increases as the length of
the bond increases.
❑ Strengths of Oxoacid
❑ Strengths of Organic Acid
❑ Structural Effects
❑ Strengths of Amines Bases
❑ Strengths of Amines Bases
❑ Resonance Effects

❑ Inductive Effects
5.10. LEWIS ACIDS AND BASES
5.11. Ion Effect in Acid-Base Equilibria

✓ The Common-Ion Effect describes the effect on an

equilibrium by a second substance that furnishes
ions that can participate in that equilibrium.
✓ The added ions are said to be common to the
equilibrium.
❑ Solutions of Weak Acids and Strong Acids

• Consider a solution that contains both 0.100

M CH3CO2H and 0.100 M HCl.
CH3CO2H + H2O CH3CO2- + H3O+

(0.100-x) M xM xM

HCl + H2O Cl- + H3O+

0.100 M 0.100 M

[H3O+] = (0.100 + x) M essentially all due to HCl

 Acetic Acid and Hydrochloric Acid

0.1 M CH3CO2H 0.1 M CH3CO2H 0.1 M CH3CO2H +

+ 0.1 M CH3CO2Na
0.1 M HCl
EXAMPLE 5-1
Demonstrating the Common-Ion Effect: Solution of a
weak Acid and a Strong Acid.
(a) Determine [H3O+] and [CH3CO2-] in 0.100 M CH3CO2H.
(b) Then determine these same quantities in a solution that is
0.100 M in both CH3CO2H and HCl.

CH3CO2H + H2O → H3O+ + CH3CO2-

[H3O+] = [CH3CO2-] = 1.310-3 M

Slide 65 of 45 General Chemistry: Chapter 17 Prentice-Hall © 2007

EXAMPLE 5-1
CH3CO2H + H2O → H3O+ + CH3CO2-

Initial concs.
weak acid 0.100 M 0M 0M
strong acid 0M 0.100 M 0M
Changes -x M +x M +x M
Equilibrium (0.100 - x) M (0.100 + x) M xM
Concentration
Assume x << 0.100 M, 0.100 – x  0.100 + x  0.100 M
EXAMPLE 5-1
CH3CO2H + H2O → H3O+ + CH3CO2-
Eqlbrm conc. (0.100 - x) M (0.100 + x) M xM
Assume x << 0.100 M, 0.100 – x  0.100 + x  0.100 M

[H3O+] [CH3CO2-] x · (0.100 + x)

Ka= =
[C3CO2H] (0.100 - x)
x · (0.100)
= = 1.810-5
(0.100)
[CH3CO2-] = 1.810-5 M compared to 1.310-3 M.
Le Châtelier’s Principle
❑ Suppression of Ionization of a Weak Acid
❑ Suppression of Ionization of a Weak Base
❑ Solutions of Weak Acids and Their Salts
❑ Solutions of Weak Bases and Their Salts
5.12. Buffer Solutions

 Two component systems that change pH only

slightly on addition of acid or base.
• The two components must not neutralize each other but
must neutralize strong acids and bases.
 A weak acid and it’s conjugate base.
CH3COOH/CH3COONa
 A weak base and it’s conjugate acid
NH3/NH4Cl
 Buffer Solutions
 Consider [CH3CO2H] = [CH3CO2-] in a solution.

[H3O+] [CH3CO2-]
Ka= = 1.810-5
[CH3CO2H]

[CH3CO2-]
[H3O+] = Ka = 1.810-5
[CH3CO2H]

pH = -log[H3O+] = -logKa = -log(1.810-5) = 4.74

Pure Water Has No Buffering Ability
❑ How A Buffer Works
❑ The Henderson-Hasselbalch Equation

• A variation of the ionization constant expression.

• Consider a hypothetical weak acid, HA, and its salt NaA:
[H3O+] [A-]
HA + H2O A- + H3O+ Ka=
[HA]
[A-] [A-]
Ka= [H3O+] -logKa= -log[H3O+]-log
[HA] [HA]
[A-] [A-]
pKa = pH - log pH = pKa + log
[HA] [HA]

[conjugate base]
pH = pKa + log
[acid]
 Henderson-Hasselbalch Equation
[conjugate base]
pH= pKa + log
[acid]

• Only useful when you can use initial concentrations

of acid and salt.
– This limits the validity of the equation.
• Limits can be met by:

[A-]
0.1 < < 10
[HA]
[A-] > 100Ka and [HA] > 100Ka
❑ Preparing a Buffer Solution
EXAMPLE 5.2
Preparing a Buffer Solution of a Desired pH. What mass of
NaC2H3O2 must be dissolved in 0.300 L of 0.25 M HC2H3O2 to
produce a solution with pH = 5.09? (Assume that the solution
volume is constant at 0.300 L)
Equilibrium expression:
HC2H3O2 + H2O C2H3O2- + H3O+
[C2H3O2-]
Ka= [H3O+] = 1.810-5
[HC2H3O2]
[H3O+] = 10-5.09 = 8.110-6
[HC2H3O2] = 0.25 M
Solve for [C2H3O2-]
EXAMPLE 5.2

-]
[HC2H3O2] 0.25
[C2H3O2 = Ka = 1.810-5 = 0.56 M
[H3 O+] 8.110-6

0.56 mol 1 mol NaC2H3O2

mass C2H3O2 = 0.300 L 
- 
1L 1 mol C2H3O2-

82.0 g NaC2H3O2
 = 14 g NaC2H3O2
1 mol NaC2H3O2
❑ Six Methods of Preparing Buffer Solutions
❑ Calculating Changes in Buffer Solutions
 Calculating pH Changes in a Buffer Solution
What are the effects on the pH of adding (a) 0.0060 mol HCl and (b) 0.0060 mol NaOH to
0.300 L of a buffer solution that is 0.25 M CH3COOH and 0,65 M CH3COONa
❑ Buffer Capacity and Range

• Buffer capacity is the amount of acid or base that

a buffer can neutralize before its pH changes
appreciably.
– Maximum buffer capacity exists when [HA] and [A-]
are large and approximately equal to each other.
• Buffer range is the pH range over which a buffer
effectively neutralizes added acids and bases.
– Practically, range is 2 pH units around pKa.
 5.13. Acid-Base Indicators
• Color of some substances depends on the pH.
HIn + H2O In- + H3O+

✓ In the acid form the color appears to be the acid color.

✓ In the base form the color appears to be the base color.
✓ Intermediate color is seen in between these two states.
✓ The complete color change occurs over about 2 pH units.
❑ Indicator Colors and Ranges
5.14 Neutralization Reactions and Titration Curves

• Equivalence point:
– The point in the reaction at which both acid and
base have been consumed.
– Neither acid nor base is present in excess.
• End point:
– The point at which the indicator changes color.
• Titrant:
– The known solution added to the solution of
unknown concentration.
• Titration Curve:
– The plot of pH vs. volume.
❑ Titration of a Strong Acid with a Strong Base
❑ Titration of a Strong Acid with a Strong Base
❑ Titration of a Strong Acid with a Strong Base

✓ The pH has a low value at the beginning.

✓ The pH changes slowly:

until just before the equivalence point.

✓ The pH rises sharply:

perhaps 6 units per 0.1 mL addition of titrant.

✓ The pH rises slowly again.

✓ Any Acid-Base Indicator will do.

As long as color change occurs between pH 4 and 10.
❑ Titration of a Strong Acid with a Strong Base

➢ The titration of a 25.00 mL of 0.100 M HCl with 0.100 M

NaOH.
➢ Phenolphthalein indicator

92
❑ Titration of a Strong Base with a Strong Acid
❑ Titration of a Weak Acid with a Strong Base
❑ Titration of a Weak Acid with a Strong Base
Calculating Points on a Titration Curve: Weak Acid
Titrated with a Strong Base
❑ Titration of a Weak Acid with a Strong Base
❑ Titration of a Weak Acid with a Strong Base
❑ Diprotic titration

10.0 mL of H3PO4 0.100 M with 0.100 M NaOH

❑ Diprotic titration
❑ Diprotic titration
 Equivalent weight, Normality

❑ The Equivalent weight or gram equivalent 𝑴

weight is the mass which combines with or 𝑬𝒘 =
𝒏
displaces 1.008 gram of hydrogen or 8.0
grams of oxygen.
❑ Equivalent: The amount of substance 𝑬𝒒 =
𝒎
= 𝒏
𝒎
which react or displace with 1 mol of 𝑬𝒘 𝑴

hydrogen ion

𝑬𝒒
❑ Normality (CN or N): the equivalent per liter 𝑵= = 𝒏. 𝑪𝑴
𝑽
of solution
❑ Equivalent law: 𝑽𝟏 . 𝑵𝟏 = 𝑽𝟐 . 𝑵𝟐

105