Chapter 16

Equilibria in Solutions of Weak

Acids and Bases
Brady and Senese
5th Edition
Delivered by
Ida Munfarida, M.Si, M.T
TL UINSA

1
Index
16.1 Ionization constants can be defined for weak
acids and bases
16.2 Calculations can involve finding or using Ka
and Kb
16.3 Salt solutions are not neutral if the ions are
weak acids or bases
16.4 Simplifications fail for some equilibrium
calculations
16.5 Buffers enable the control of pH
16.6 Polyprotic acids ionize in two or more steps
16.7 Acid-base titrations have sharp changes in pH at
the equivalence point
2
Acids and Ka

HA(aq) + H2O H3O+(aq) + A–(aq)

• All acids undergo ionization reaction with water
• Weak acids undergo this reaction as an equilibrium
process governed by the acid ionization constant, Ka.
• Strong acids are 100% efficient in non-reversible
reaction
• Ka are tabulated in table 16.1, as are pKa
• Ka = 10-pKa pKa = -log Ka
 H +   A− 
Ka =    
 HA
16.1 Ionization constants can be defined for weak acids and bases 3
Bases and Kb

B(aq) + H2O BH+(aq) + OH–(aq)

• Undergo ionization reaction with water
• Weak bases undergo this reaction as an equilibrium
process governed by the base ionization constant, Kb
• Kb and pKb are tabulated in table 16.2
• Kb = 10-pKb pKb = -log Kb
 BH +  OH − 
Kb =   
 B
16.1 Ionization constants can be defined for weak acids and bases 4
Your Turn!
Which of the following is a product in the acid
ionization of H2CO3?
A. HCO3-
B. H2O
C. CO32-
D. All of these
E. None of these

16.1 Ionization constants can be defined for weak acids and bases 5
For Conjugate Pairs Kw = Ka × Kb

16.1 Ionization constants can be defined for weak acids and bases 6
Learning Check

What is the value of Kb for the following weak

conjugate bases?
▪ NaF
▪ Kw = Ka × Kb Ka for HF = 6.8 × 10-4
▪ 1.5 × 10-11
▪ NaCN
▪ Kw = Ka × Kb Ka for HCN = 6.2 × 10-10
▪ 1.6 × 10-5

16.1 Ionization constants can be defined for weak acids and bases 7
Learning Check

What is the value of Ka for the following weak

conjugate acids?
▪ NH4Cl
▪ Kw = Ka × Kb Kb for NH3 = 1.8 × 10-5
▪ 5.6 × 10-10
▪ C6H5NH3NO3
▪ Kw =Ka × Kb Ka = 4.1 × 10-10
▪ 2.4 × 10-5

16.1 Ionization constants can be defined for weak acids and bases 8
Your Turn!
Given that Ka for benzoic acid (C6H5CO2H) = 6.28 × 10-5,
what is the Kb for sodium benzoate, NaC6H5CO2, a
common preservative?
A. 6.28 × 10-5
B. 6.28 × 10-19
C. 1.59 × 10-10
D. None of these

16.1 Ionization constants can be defined for weak acids and bases 9
Determining the pH of Aqueous Weak Acid
Solutions
• Dominant equilibrium is Ka reaction
▪ Write the net ionic equation
▪ Look up the Ka value for the acid
▪ Set up ICE table
▪ Solve for x
• Calculate pH from the hydronium concentration at
equilibrium

16.2 Calculations can involve finding or using Ka and Kb 10

Simplifications: Dropping x Term
• If the K for the reaction is small, the change to
reach equilibrium (x term) is small (less than 5%
of the value of the starting concentration)
• In binomial terms, the x variable term may be
dropped in favor of the concentration (constant)
• You must perform a proof to show that the
dropped x was justified
?


dropped x term
0.05
constant of binomial

16.2 Calculations can involve finding or using Ka and Kb 11

Learning Check
Determine the pH of 0.1 M solutions of:
HC2H3O2 HC2H3O2(aq) + H2O H3O+(aq) + C2H3O2-
• Ka = 1.8 × 10-5 (aq)
x2 0.1 M N/A 0 0
= 1.8  10−5 I
0.1 -x -x +x +x
C
x = 1.34 × 10-3 M
(0.1 - x) ≈ 0.1 N/A x x
pH = 2.87 E

HCN HCN(aq) + H2O H3O+(aq) + CN-(aq)

• Ka = 6.2 × 10-10 I 0.1 M N/A 0 0
x2 −10
= 6.2  10 C -x -x +x +x
0.1
x = 7.87 × 10-6 M E (0.1 - x) ≈ 0.1 N/A x x
pH = 5.10
16.2 Calculations can involve finding or using Ka and Kb 12
Determining the pH of Base Solutions
• Dominant equilibrium is Kb reaction
▪ Write the net ionic equation
▪ Set up ICE table for starting quantities
▪ Solve for x
• Calculate pOH from the [OH-] at equilibrium, and
convert to pH

16.2 Calculations can involve finding or using Ka and Kb 13

Learning Check:
Determine the pH of 0.1 M solutions of:
• N2H4 N2H4(aq) + H2O OH-(aq) + N2H5+(aq)
• Kb = 1.7 × 10-6 0.1 M N/A 0 0
I
x2
= 1.7  10−6 C -x -x +x +x
0.1
x = 4.12 × 10-4 M E (0.1-x) ≈ 0.1 N/A x x
pOH = 3.38 pH = 10.62

• NH3 NH3(aq) + H2O H3O+(aq) + CN-(aq)

• Kb = 1.8 × 10-5 I 0.1 M N/A 0 0
x2
= 1.8  10−5 C -x -x +x +x
0.1
x = 1.34 × 10 M
-3
E (0.1-x) ≈ 0.1 N/A x x
pOH = 2.87 pH = 11.13
16.2 Calculations can involve finding or using Ka and Kb 14
Your Turn!
What is the pH of a 0.30 M solution of phenol
(C6H5OH), an ingredient in some older
mouthwashes? Ka = 1.3 × 10-10?
A. 9.2
B. 0.52
C. 9.4
D. None of these 5.20

16.2 Calculations can involve finding or using Ka and Kb 15

Percent Ionization
• Weak acids ionize some amount less than 100%.
• The percentage to which it is ionized may be
calculated using the Ka for the acid and the
equilibrium concentrations
• Percentage ionized varies with starting
concentration, even for the same acid

moles ionized per liter

% ionization =  100
available moles per liter

16.2 Calculations can involve finding or using Ka and Kb 16

Learning Check
Determine the % ionization of 0.2 M solution of
HC2H3O2
HC2H3O2(aq) + H2O H3O+(aq) + C2H3O2-(aq)
▪ Ka = 1.8 × 10-5
I 0.2 M N/A 0 0
x2
= 1.8  10−5 C -x -x +x +x
0.2
E (0.2 - x) ≈ 0.2 N/A x x
x = 1.90 × 10-3 M

moles ionized per liter

% ionization =  100
available moles per liter
x
 100 = % 0.95% ionized
0.2
16.2 Calculations can involve finding or using Ka and Kb 17
Learning Check
Determine the % ionization of 0.1 M solution of
HC2H3O2
HC2H3O2(aq) + H2O H3O+(aq) + C2H3O2-(aq)
• Ka=1.8×10-5
I 0.1 M N/A 0 0
x2
= 1.8  10−5 C -x -x +x +x
0.1
E (0.1-x) ≈ 0.1 N/A x x
x = 1.34 × 10-3 M
moles ionized per liter
% ionization =  100
available moles per liter
x
 100 = % 1.3% ionized
0.1
16.2 Calculations can involve finding or using Ka and Kb 18
Your Turn!
What is the % ionization of 0.10 M HOCl?
(Ka = 3.0 × 10-8)
A. 0.5%
B. 0.05%
C. 5.5 × 10-6%
D. None of these

16.2 Calculations can involve finding or using Ka and Kb 19

Your Turn!
What is the % ionization of 0.50 M HOCl?
(Ka = 3.0 × 10-8)
A. 0.12%
B. 6.0 × 10-6 %
C. 0.06%
D. None of these 0.025%

16.2 Calculations can involve finding or using Ka and Kb 20

Learning Check
The pH of a 0.50 M solution
of an acidic drug, HD, is 3.5. Given the pH, we find
What is the value of the Ka the value of x = 10-pH
for the drug? x = 10-3.5 = 3.16 × 10-4
x2
HD + H2O H3O+ + D- = Ka
0.50 − x

(3.16 10 )
2
I 0.50 NA 0 0 −4

= Ka
C -x -x +x +x ( 0.5 − 3.16 10 ) −4

E 0.50 - x NA x x
Ka = 2.0 × 10-7
16.2 Calculations can involve finding or using Ka and Kb 21