1

Acid-Base
Equilibria
 2

ACIDS BASES
Taste sour Taste bitter
Turn blue litmus paper to Turn red litmus paper to
red blue
React with metals Do not react with metals
Feel like water Feel slippery
Become less acidic when Become less basic when
combined with a base combined with an acid
Acids 3
Bases 4
 5

ACIDS BASES
Arrhenius Increase [H+] in Increase [OH–] in
definition solution solution

Bronsted-Lowry Proton (H +)
Proton (H+) donor
definition acceptor

Electron pair Electron pair

Lewis definition
acceptor donor
Arrhenius Definition 6

• Arrhenius acids
• Substances that ionize in water to produce H+
• eg
HCl(aq) H+(aq) + Cl–(aq)

• Arrhenius bases
• Substances that ionize in water to produce OH–
• eg
NaOH(aq) Na+(aq) + OH–(aq)
Brønsted-Lowry Definition 7

• Brønsted-Lowry acids - proton donors

• Brønsted-Lowry bases - proton acceptors
• eg
HCl(aq) + H2O(l) H3O+(aq) + Cl–(aq)

B-L acid B-L base

NH3(aq) + H2O(l) NH4+(aq) + OH–(aq)

B-L base B-L acid

Lewis Definition 8

• Lewis acids – electron pair acceptors

• Lewis bases – electron pair donors
• eg.
H+(aq) + NH3(aq) NH4+(aq)
Lewis Definition 9

• A more general definition

• not limited to Brønsted-Lowry acids/bases
• eg
Autoprotolysis of Water 10

H2O(l) + H2O(l) H3O+(aq) + OH–(aq)

Ionization Constant of Water 11

• H2O(l) + H2O(l) H3O+(aq) + OH–(aq)

• Equilibrium constant expression:

• Keq = [H3O+][OH–]
= 1.0 × 10–14 at 25 °C
= Kw
Concentration of H3O+ in pure 12

water
• H2O(l) + H2O(l) H3O+(aq) + OH–(aq)

• For pure water at 25 °C

• [H3O+] = [OH–] (accdg. to the balanced eqn.)
• Then,
• [H3O+] = [OH–] = 𝟏. 𝟎 × 𝟏𝟎−𝟏𝟒
= 1.0 × 10–7 M
pH 13
• pH = –log [H3O+]
• For pure water at 25 °C:
• pH = –log (1.0 × 10–7)
= 7.0
(at different temperatures, pH of pure water is not 7.0)

• pH = 7.0 (neutral)
• pH < 7.0 (acidic)
• pH > 7.0 (basic)
pKw, pOH 14

• Kw = [H3O+][OH–] = 1.0 × 10–14 M

• Taking the –log of both sides

• –log Kw = (–log [H3O+]) + (–log [OH–])
= (–log 1.0 × 10–14)
• pKw = pH + pOH = 14.0
Conjugate Acid-Base Pairs 15

• Conjugate Base
• The species that results when an acid gives
off its acidic proton (H+)
• Conjugate Acid
• The species that results when a base accepts
a proton given off by the acid

HCl(aq) + H2O(l) H3O+(aq) + Cl–(aq)

acid base conjugate acid conjugate base
Strengths of Acids and Bases 16

Strong acid – dissociates more or less

completely when it dissolves in water.
conjugate bases of strong acids are weaker than
water

Weak acid – dissociates only slightly when it

dissolves in water
conjugate bases of weak acids are stronger than
water
Strong Acids and Bases 17

• Strong Acids
• HCl, HI, HBr, HNO3, HClO4
• H2SO4 (first ionization only)
• Strong Bases
• LiOH, NaOH, KOH, RbOH, CsOH
• Ca(OH)2, Ba(OH)2, Sr(OH)2
Systematic Approach to Solve 18

Acid-Base Equilibrium Problems

1. list any known values  given in the problem
2. list what it is you are attempting to solve
3. write balanced equations for all equilibria
4. write down all equilibrium expressions along with their
constants
5. develop mass and/or charge balance expressions
6. count number of equations and unknowns  if you have
as many unique equations as unknowns, then the problem
is solvable
Proton Balance Equation, PBE 19

• Matches the concentration of species which have

released protons with those which have
consumed.

# protons consumed = # protons released

proton rich = proton poor

Proton Balance Equation 20

PRACTICE:
Write the proton balance equation of the following:

1. H2O
2. strong acid - HBr
3. strong base - KOH
4. weak acid (monoprotic) - HCN
5. weak base (monobasic) - NH3
Proton Balance Equation 21

 ANSWERS
1. [H+] = [OH-]
2. [H+] = [OH-] + [Br-], Br- is a measure of H+ released
3. [H+] + [K+] = [OH-], K+ is a measure of OH- released
4. [H+] = [OH-] + [CN-]
5. [H+] + [NH4+] = [OH-]
Mass Balance Equation, MBE 22

• Equations that relate the equilibrium concentrations of

species in a solution to each other and the formal
(analytical) concentrations of the solutes.

• It states thatCHA  HA  A  ,

that is analytical
concentration of an acid or base is equal to the sum of
concentrations of the protonated and unprotonated
species.
Charge Balance Equation, CBE 23

• Equations that express the electrical neutrality of a

solution by equating the molar concentrations of the
positive and negative charges.

sum (+) charge = sum (-) charge

• Neutral species are not included

• Eg. For a 0.1 M NaHCO3 solution

CBE: [Na+]+[H3O+] = [OH-]+[HCO3-]+2[CO32-]

Sample Problem 24

 Using the systematic approach, what is the pH

of a 0.040 M HCl solution?
 Answer: 1.40

 Using the systematic approach, what is the pH

of a 0.040 M NaOH solution?
 Answer: 12.60
Solution: HCl(aq) → Cl-(aq) + H3O+(aq) 25
H2O(l) + H2O(l) OH-(aq) + H3O+(aq)
PBE: [H3O+] = [OH-] + [Cl-]
MBE: CHCl = [Cl-]
𝐾𝑤 = 𝐻3 𝑂+ 𝑂𝐻−
[H3O+] = [OH-] + [Cl-]
+ 𝐾𝑤 −
[𝐻3𝑂 ] = + [𝐶𝑙 ]
[𝐻3𝑂+]
+ 𝐾𝑤
[𝐻3𝑂 ] = + 𝐶𝐻𝐶𝑙
[𝐻3𝑂+]

Multiply both sides with [H3O+]

 + 2 + 26
𝐻3𝑂 = 𝐾𝑤 + 𝐶𝐻𝐶𝑙 𝐻3𝑂
+
𝑙𝑒𝑡 𝑥 = [𝐻3𝑂 ]
𝒙2 = 𝐾𝑤 + 𝐶𝐻𝐶𝑙𝒙
0 = −𝒙2 + 𝐶𝐻𝐶𝑙𝒙 + 𝐾𝑤
0 = −𝒙2 + 0.040𝒙 + 1x10−14
+
𝒙 = 0.04 = [𝐻3𝑂 ]
𝑝𝐻 = − log 0.04
𝑝𝐻 = 1.40
Weak Acids and Bases 27

• Do not dissociate completely in solution

• Eg.

HCN(aq) + H2O(l) H3O+(aq) + CN–(aq)

• In an aqueous solution of HCN,

species present would be H3O+, CN–,
H2O (solvent) and unionized HCN
Weak Acids 28

• For a generalized acid dissociation reaction:

HA(aq) + H2O(l) A–(aq) + H3O+(aq)

• The equilibrium constant expression would be

𝑯𝟑 𝑶+ 𝑨−
𝑲𝒂 =
𝑯𝑨

• Ka = acid dissociation constant

• The higher the Ka value, the stronger the acid
Weak Bases 29

• For a generalized base dissociation reaction:

A–(aq) + H2O(l) HA(aq) + OH–(aq)

• The equilibrium constant expression would be

𝑯𝑨 𝑶𝑯−
𝑲𝒃 =
𝑨−

• Kb = base dissociation constant

• The higher the Kb value, the stronger the base
Sample Problems 30

1. Using the systematic approach, what is the

pH of a 0.200 M HCN solution? The Ka for HCN
is 4.9 × 10–10.
Solution:
31
HCN(aq) + H2O(l) CN-(aq) + H3O+(aq)
H2O(l) + H2O(l) OH-(aq) + H3O+(aq)
PBE: [H3O+] = [OH-] + [CN-]
MBE: CHCN = [HCN] + [CN-]
𝐻3 𝑂+ 𝐶𝑁 −
𝐾𝑎 =
𝐻𝐶𝑁
𝐾𝑤 = 𝐻3 𝑂+ 𝑂𝐻−
Since the solution is acidic, assume that [OH-] is very low.
[H3O+] = [OH-] + [CN-]
+
𝑙𝑒𝑡 𝑥 = [𝐻3𝑂 ]
 𝑥2 𝑥2 𝑥2 32
𝐾𝑎 = = -
=
𝐻𝐶𝑁 𝐶𝐻𝐶𝑁 − [CN ] 𝐶𝐻𝐶𝑁 − 𝑥
𝑥2
𝐾𝑎 =
𝐶𝐻𝐶𝑁 − 𝑥
𝐾𝑎𝐶𝐻𝐶𝑁 − 𝐾𝑎𝑥 = 𝑥 2
0 = 𝑥 2 + 𝐾𝑎𝑥 − 𝐾𝑎𝐶𝐻𝐶𝑁
0 = 𝒙2 + 4.8x10−10 𝒙 − 9.8x10−11
+
𝒙= 9.899x10−6 = [𝐻3𝑂 ]
𝑝𝐻 = − log 9.899x10−6
𝑝𝐻 = 5.00
Sample Problems 33

2. Using the systematic approach, what is the pH

of a 0.150 M NH3 solution? The Kb for this weak
base is 1.8 × 10–5.

Answer: pH = 11.21
Percent Ionization 34

amount dissociated
% ionization= ×100
initial concentration

Problem:
1. What is the % ionization of a 0.150 M solution
of NH3? The Kb for this weak base is 1.8 × 10–5.

Answer: % ionization = 1.09%

Percent Ionization 35

Problem:
2. The pH of a 0.25 M solution of formic
acid HCOOH at 25 °C is 2.38. Calculate
the % ionization and Ka for formic acid at
this temperature.
[H3O+] = antilog (-2.38) = 4.169x10-3
• Answer: % ionization = 1.67 %
Ka = 7.07 × 10–5
Relationship between Ka and Kb 36

𝑯𝟑 𝑶+ 𝑨− 𝑯𝑨 𝑶𝑯−
𝑲𝒂 = 𝑲𝒃 =
𝑯𝑨 𝑨−

𝑯𝟑 𝑶+ 𝑨− 𝑯𝑨 𝑶𝑯−
𝑲𝒂 × 𝑲𝒃 = ×
𝑯𝑨 𝑨−

𝑲𝒂 × 𝑲𝒃 = 𝑯𝟑 𝑶+ 𝑶𝑯−

𝑲 𝒘 = 𝑲𝒂 × 𝑲𝒃
Hydrolysis of Salts 37

• Ions produced from salts can react with

water (hydrolysis) to produce H3O+ or OH–

• Can exhibit acidic or basic properties

Salts formed from neutralization of 38

a strong acid and a strong base

• eg. NaCl: NaCl → Na+ + Cl–
• Na+ + H2O → no reaction
• Cl– + H2O → no reaction

• NaCl solution is neutral (pH = 7.00)

• Other examples: KNO3, CaCl2

Salts formed from neutralization of 39

a strong acid and a weak base

• eg. NH4Cl: NH4Cl → NH4+ + Cl–
• NH4+ + H2O ⇌ NH3 + H3O+
• Cl– + H2O → no reaction
• cation hydrolyzes
• NH4Cl solution is acidic

• Other examples: NH4Br, NH4NO3

Salts formed from neutralization of 40

a weak acid and a strong base

• eg. KCN: KCN → K+ + CN–
• K+ + H2O → no reaction
• CN– + H2O ⇌ HCN + OH–
• anion hydrolyzes
• KCN solution is basic

• Other examples: Na2C2O4, BaF2

Salts formed from neutralization of 41

a weak acid and a weak base

• Both the cation and anion hydrolyzes

• Ka > Kb : acidic solution
• Ka < Kb : basic solution
• Ka = Kb : neutral solution
Sample Problems 42

• Calculate the pH (using systematic method) of a

0.30 M NaF solution. (Ka of HF = 7.2 ×10–4)
answer: 8.31

• Calculate the pH (using systematic method) of a

0.10 M NH4Cl solution. (Kb NH3 = 1.8 × 10–5)
answer: 5.13
Solution:
NaF(aq) → F-(aq) + Na+(aq) 43
F-(aq) + H2O(l) HF(aq) + OH-(aq)
H2O(l) + H2O(l) OH-(aq) + H3O+(aq)
PBE: [OH-] = [H3O+] + [HF]
MBE: CNaF = [HF] + [F-]
𝐻𝐹 𝑂𝐻 − 𝐾𝑤
𝐾𝑏 = −
=
𝐹 𝐾𝑎
𝐾𝑤 = 𝐻3 𝑂+ 𝑂𝐻−
Since the solution is basic, assume that [H3O+] is very low.
[OH-] = [H3O+] + [HF]
𝑙𝑒𝑡 𝑥 = [𝑂𝐻 − ]
 𝐻𝐹 𝑂𝐻 − 𝐾𝑤
𝐾𝑏 = = 44
𝐹 − 𝐾𝑎
𝑥2 𝑥2 𝑥2
𝐾𝑏 = −
= =
𝐹 𝐶𝑁𝑎𝐹 − [𝐻𝐹] 𝐶𝐻𝐶𝑁 − 𝑥
𝐾𝑎𝐶𝐻𝐶𝑁 − 𝐾𝑎𝑥 = 𝑥 2
0 = 𝑥 2 + 𝐾𝑎𝑥 − 𝐾𝑎𝐶𝐻𝐶𝑁
0 = 𝒙2 + 1.3889x10−11 𝒙 − 4.1667x10−12
𝒙 = 2.0412x10−6 = [𝑂𝐻 − ]
𝑝𝑂𝐻 = − log 2.0412x10−6
𝑝𝑂𝐻 = 5.69
𝑝𝐻 = 8.31
Polyprotic Acids and Bases 45

• H2B – Diprotic Acids and Bases

[H3O  ][HB  ]
H2B + H2O  H3O+ + HB- K a1 
[H2B]

[H3O  ][B 2  ]
K a2 
HB- + H2O  H3O+ + B2- [HB ]
Polyprotic Acids and Bases 46

• Take Note!

Usually K >>> K
a1 a2

Ka1  H3O+ from neutral species

Ka2  H3O+ from a charged species
Polyprotic Acids and Bases 47

Example

Alanine Hydrochloride is a salt consisting of the

diprotic weak acid H2L+ and Cl-. Calculate the pH of
0.10 M H2L+ solution (Ka1 = 4.487 x 10-3, Ka2 = 1.358 x
10-10).

K a1 K a2
H2L+ HL L-
K b2 K b1
Polyprotic Acids and Bases 48

 pertinent equilibria
[HL][H3O  ]
H2L+ + H2O  HL + H3O+ K a1  
[H2L ]

HL + H2O  L- + H3O+ [L ][H3O  ]

K a2 
[HL ]
2H2O  H3O+ + OH- 
Kw  [H3O ][OH ] 
Polyprotic Acids and Bases 49

 Assume that any solution containing an

appreciable quantity of H2L+ will contain
essentially no L- (Since Ka1 >>> Ka2)

PBE [H3O+] = [OH-] + [HL]

MBE CH L  [ H 2 L ]  [ HL]
2
Polyprotic Acids and Bases 50

 Since H2L+ is a weak acid

PBE [H3O+] = [OH-] + [HL]

MBE CH L  [ H 2 L ]  [ HL]
2

[ H 2 L ]  CH L  [ HL]
2

[ H 2 L ]  CH L  [ H 3O  ]
2
Polyprotic Acids and Bases 51

 Substituting and simplifying equations

[HL][H3O  ]
K a1 
[H2L ]
 
[ H 3O ][ H 3O ]
K a1 
CH L  [ H 3O  ]
2
Polyprotic Acids and Bases 52

 Solving the quadratic equation

[H3O  ]  1.91  10 2 M
pH  1.72
Polyprotic Acids and Bases 53

Example

Calculate the pH of 0.10 M L- solution

(Ka1 = 4.487 x 10-3, Ka2 = 1.358 x 10-10).

Answer: 11.43
 Kw 1.0  10 14 5
54
L- + H2O  HL + OH- K b1    7.364  10
K a 2 1.358  10 10

HL + H2O  H2 L+ + OH- Kw 1.0  10 14 12

K b2    2.229  10
K a1 4.487  10  3

2H2O  H3O+ + OH- Kw  [H3O ][OH ] 

 Assume that any solution containing an appreciable quantity of L-

will contain essentially no H2L+ (Since Kb1 >>> Kb2)
PBE: [H3O+] + [HL] = [OH-], since solution is basic, cancel H3O+
MBE: CNaF = [HF] + [F-]
 55
𝐻𝐿 𝑂𝐻 − 𝐾𝑤
𝐾𝑏1 = =
𝐿− 𝐾𝑎2
𝐻𝐿 𝑂𝐻 − 𝐾𝑤
𝐾𝑏1 = −
=
𝐶𝐿− − 𝑂𝐻 𝐾𝑎2

𝑙𝑒𝑡 𝑥 = [𝑂𝐻 − ]

Solving the quadratic equation,

[OH  ]  2.677  10 3 M
[H3O  ]  3.736  10 12 M
pH  11.43
Sample problem 56

Calculate systematically the pH of 0.100 M Na2CO3

solution.

Ka1 at 25oC (H2CO3) = 4.45 x 10-4

Ka2 at 25oC (H2CO3) = 4.46 x 10-11

Answer: 11.67
Ampholytes 57


[H3O ]  K a1K a 2

For a solution of 0.10 M HL

[H3O  ]  (4.487  10 3)(1.358  10 10)  7.807  10 7 M

pH  6.11
Buffer Solutions 58

• Solutions that resist drastic changes in pH upon

addition of small amounts of acids or bases
• Can be made up of the following combinations:
• weak acid + salt containing the conjugate base
• weak base + salt containing the conjugate acid
Acidic Buffers 59

• Weak acid + a salt containing its conjugate base

• Eg. CH3COOH and NaCH3COO

• Equilibrium reaction:

CH3COOH(aq) + H2O(l) CH3COO–(aq) + H3O+(aq)

Acidic Buffers 60

• Upon addition of a small amount of acid (H3O+)

• CH3COO–(aq) + H3O+(aq)→CH3COOH(aq) + H2O(l)

• Upon addition of a small amount of base (OH–)

• CH3COOH(aq) + OH–(aq)→CH3COO–(aq) + H2O(l)
Basic Buffers 61

• Weak base + a salt containing its conjugate acid

• Eg. NH3 and NH4Cl

• Equilibrium reaction:

NH3(aq) + H2O(l) NH4+(aq) + OH–(aq)

Basic Buffers 62

• Upon addition of a small amount of acid (H3O+)

• NH3(aq) + H3O+(aq)→ NH4+(aq) + H2O(l)

• Upon addition of a small amount of base (OH–)

• NH4+(aq) + OH–(aq)→ NH3(aq) + H2O(l)
Henderson-Hasselbach Equation 63

HA(aq) + H2O(l) H3O+(aq) + A–(aq)

𝑯𝟑 𝑶+ 𝑨−
𝑲𝒂 =
𝑯𝑨

• Take – log of both sides

𝑨−
−𝒍𝒐𝒈 𝑲𝒂 = −𝒍𝒐𝒈 𝑯𝟑 𝑶+ − 𝒍𝒐𝒈
𝑯𝑨

𝑨−
𝒑𝑲𝒂 = 𝒑𝑯 − 𝒍𝒐𝒈
𝑯𝑨
Henderson-Hasselbach Equation 64

𝑨−
𝒑𝑯 = 𝒑𝑲𝒂 + 𝒍𝒐𝒈
𝑯𝑨

𝑩
𝒑𝑯 = 𝒑𝑲𝒂 + 𝒍𝒐𝒈
𝑩𝑯+
Sample problems 65

1. Calculate the pH of a buffer containing 0.60 M

CH3COOH and 0.40 M NaCH3COO.
(Ka = 1.8 × 10–5)
Answer: 4.57

2. Calculate the pH of a buffer containing 0.35 M NH3 and

0.45 M NH4Cl. (Kb = 1.8 × 10–5)
Answer: 9.15
Sample problem 66

3. Calculate the pH of a buffer prepared by mixing 200 mL

of 0.60 M NH3 and 300 mL of 0.30 M NH4Cl (Kb = 1.8 ×
10–5). What will be the pH if 0.02 mol of acid is added to
the buffer?
Answer:
pH of the buffer: 9.38
pH after adding acid: 9.21
Solution:
67
0.60 𝑀 𝑥 200 𝑚𝐿 0.30 𝑀 𝑥 300 𝑚𝐿
𝑁𝐻3 = = 0.24 𝑀 𝑁𝐻4+ = = 0.18 𝑀
500 𝑚𝐿 500 𝑚𝐿
0.02 𝑚𝑜𝑙
𝐻3 𝑂+ = = 0.04 𝑀
0.5 𝐿

NH3(aq) + H3O+(aq) NH4+(aq) + H2O(l)

Initial 0.24 M 0.04 M 0.18 M
Change -x -x +x
Equil. 0.24 - x 0 0.18 + x

𝑁𝐻3 = 0.20 𝑀
𝑁𝐻4+ = 0.22 𝑀
Sample problem 68

4. Calculate the pH change when 0.02 mol NaOH is

added to 80.0 mL of a buffer that is 0.7 M HCN and 0.5 M
NaCN (Ka = 6.2 × 10–10)
Answer:
pH of the buffer: 9.06
pH after adding NaOH: 9.43
ΔpH = 0.37
Solution:
69
0.02 𝑚𝑜𝑙
𝑂𝐻 − = = 0. 25 𝑀
0.08 𝐿

HCN(aq) + OH-(aq) CN-(aq) + H2O(l)

Initial 0.70 M 0.25 M 0.50 M
Change -x -x +x
Equil. 0.70 - x 0 0.50 + x

𝐻𝐶𝑁 = 0.45 𝑀
𝑁𝐻4+ = 0.75 𝑀