UNIT 6


Acid-Base Equilibria

maidliu 04.09.2019
 Models of Acids and Bases
• Arrhenius: acids produce H3O+ ions in aqueous
solution; bases produce OH– ions.
• Brønsted–Lowry: acids are proton (H+) donors;
bases are proton acceptors.
• Lewis: acids are electron pair acceptors; bases
are electron pair donors.
 Nature of Acids and Bases
• Acids are classified a monoprotic, diprotic, or
triprotic depending on the number of protons
each may give up.
• Ex. HCl, H2CO3, and H3PO4
• Several molecules and ions can function as either
an acid or a base (amphiprotic).
• Ex. H2PO4- + OH- HPO42- + H2O
H2PO4- + H3O+ H3PO4 + H2O

• Not all hydrogen atoms in most compounds can

be given up.
• Ex. Acetic acid, CH3COOH, gives up only one proton.
 Problem Set
1. Determine if the substances below is an acid,
a base or an amphiprotic.
A. HClO4
B. HSO4-
C. S2-
D. PO43-
E. NH4+
F. HCO3-
 Nature of Acids and Bases
HA(aq) + H2O(l) H3O+(aq) + A-(aq)
acid base conjugate conjugate
acid base

• Conjugate base is everything that remains of the

acid molecule after a proton is lost.
• Conjugate acid is formed when the proton is
transferred to the base.
Acids and Conjugate Bases
 Problem Set
2. Identify the acid-conjugate base pair in the
following equilibria:
A. CH3COOH + H2O CH3COO- + H3O+
B. NH3 + H2O NH4+ + OH-
C. LiOH + HBr → H2O + LiBr
D. HSO4−+HCO3− SO42−+ H2CO3
 Nature of Acids and Bases
• 
 Nature of Acids and Bases
• 
 Nature of Acids and Bases
• [H3O+] and [OH-] for most solutions are numbers
with negative exponents, these concentrations
can be express as pH and pOH, respectively,
where:
pH = -log [H3O+]
pOH = -log [OH-]
• Acidic and basic solutions can be defined as:
• Acidic solution pH < 7.0
• Basic solution pH > 7.0
• Neutral solution pH = 7.0
 pH/pOH Calculations
• 
Problem Set
3. Complete the table:

[H+], M [OH-], M pH pOH

  3.2 x 10—11    
5.0 x 10—3      
    13.40  
      10.80
 Strengths of Acids and Bases
• Strong acid/base: it reacts completely or almost
completely with water to form H3O+/OH- ions
• Ionization equilibrium lies far to the right
• Yields a weak conjugate base/acid
 Strengths of Acids and Bases
• Weak acid/base: it dissociates only partially in
water to produce H3O+/OH- ions.
• Ionization equilibrium lies far to the left.
• Weaker the acid, stronger its conjugate base.
• Weaker the base, stronger its conjugate acid.
Strengths of Acids and Bases
 Strengths of Acids
• 
 Strengths of Acids
• Acid ionization constant, Ka, is a quantitative
measure of acid strength.
• Ka value is proportional to acid strength
• Because Ka for weak acids are numbers with
negative exponents, it is commonly express as
pKa:
pKa = -logKa
• pKa is inversely proportional to acid strength
Acid Ionization Constant
 Strengths of Bases
• 
 Strengths of Bases
• Base ionization constant, Kb, is a quantitative
measure of base strength.
• Kb value is proportional to base strength
• Because Kb for weak bases are numbers with
negative exponents, it is commonly express as
pKb:
pKb = -logKb
• pKb is inversely proportional to base strength
 Relation between Ka and Kb
• HA in aqueous solution is acidic:
HA(aq) + H2O(aq) A-(aq) + H3O+(aq)
 

• An equation for A- acting as an acid as:

A-(aq) + H2O(aq) HA(aq) + OH-(aq)
 
 Relation between Ka and Kb
• Add the two equations:
H2O(aq) + H2O(aq) H3O+(aq) + OH-(aq)

• The equilibrium constant of the resulting equation

is the product of the two equilibrium constants:
Kw = [H3O+][OH-] = Ka x Kb = 1.0 x 10-14

• This relationship can be used to determine Ka for

a weak acid from a measurement of Kb for its
conjugate base, and vice versa
 Relative Strengths of Acids and Bases
Ka Conjugate Acid Conjugate Base Kb

very large HCl (strong acid) Cl−

very small
H3O+ H2O
6.9 x 10− 4 HF F− 1.4 x 10− 11
1.8 x 10− 5 CH3COOH CH3COO − 5.6 x 10− 10
5.6 x 10− 10 NH4+ NH3 1.8 x 10− 5
H2O OH−
very small OH− (strong base) O2− very large
 Problem Set
4. In each pair, which is the stronger acid? will
produce a stronger conjugate base?
A. Pyruvic acid (pKa = 2.49) or lactic acid (pKa =
3.08)
B. Citric acid (pKa = 3.08) or phosphoric acid (pKa
= 2.10)
C. Benzoic acid (Ka = 6.5 x 10-5) or lactic acid (Ka
= 8.4 x 10-4)
D. Carbonic acid (Ka = 4.3 x 10-7) or boric acid (Ka
= 7.3 x 10-10)
pH Calculations
•Identifying acid/base strength is important
in pH calcualtions
• Is it an equilibrium reaction or a reaction
that will go essentially to completion?
• Strong acid/base is major H3O+/OH-; hence,
pH calculation will be based in the conc. of
strong acid/base
• pH calculation of weak acid/base will be
based on its ionization in water. To solve for
pH, use the Ka/Kb and follow the same
steps in solving equilibrium problems.
 Problem Set
5. Calculate the pH of a 1.5 x 10–2 M solution of
HNO3.

Answer: pH 1.82
 Problem Set
6. Calculate the pH of a 2.5 x 10–4 M solution of
HCl.

Answer: pH 3.60
 Problem Set
7. Calculate the pH of a 3.5 x 10–3 M solution of
NaOH.

Answer: pH 11.54
Problem Set
8. Calculate the pH of a 0.010 M CH3COOH
solution. Ka = 1.8 x 10-5

Answer: pH 3.37
 Problem Set
9. Calculate the pH and percent dissociation of a
0.40 M nitrous acid, HNO2, solution. Ka = 4.0 x
10-4

Answer: pH 1.90, 3.2%

 Problem Set
10. Calculate the pH of a 0.1 M hypochlorous
acid solution. Ka = 3.5 x 10-8

Answer: pH 4.23
Problem Set
11. Calculate the pH of a 2.0 M ammonia
solution. Kb = 1.8 x 10-5

Answer: pH 11.78
 Equilibria of Polyprotic acids
• Acids that can furnish more than one proton.
• Always dissociates in a stepwise manner, one
proton at a time.
• The conjugate base of the first dissociation
equilibrium becomes the acid in the second step.
• For a typical weak polyprotic acid:
Ka1 > Ka2 > Ka3
• For a typical polyprotic acid in water, only the
first dissociation step is important to pH.
Equilibria of Polyprotic acids
 pH Buffer
• pH buffer solution consists of weak acid and a
salt of its conjugate base OR weak base and a
salt of its conjugate acid
• It can resists sudden change in pH when small
amounts of acid or base are added to it.
• A pH buffer is an acid or base “shock absorber.”
 pH Buffer
• How does an acetate buffer resist changes in
pH?

• If we add a strong acid, such as HCl, added H3O+ ions

react with acetate ions and are removed from solution:

• If we add a strong base, such as NaOH, added OH- ions

react with acetic acid and are removed from solution:
 pH Buffer
• To calculate pH of buffer solution: use the
Henderson-Hasselbalch equation
• A mathematical relationship between pH, pKa of the
weak acid (HA) and the concentrations of HA and its
conjugate base A-.
• It is derived taking the logarithm of this
equation:

• To give:
 Problem Set
12. Calculate the pH of a 0.500 L buffer solution
composed of 0.700 M formic acid (HCOOH) and
0.500 M sodium formate (HCOONa). Ka = 1.77 x
10-4

Answer: pH 3.61
 Problem Set
13. Calculate the pH of a buffer solution that
initially consists of 0.050 M NH3 and 0.035 M
NH4Cl. Kb = 1.8 x 10-5

Answer: pH 9.41
Assignment
Bettelheim
8-20, a-f
8-41, a-d
8-66, a-b
8-82
8-112