Chapter 9

Aqueous solution and

chemical equilibria
 Acid and base
• Bronsted-Lowry acid-base concept:
- Acid: proton donor: H2O, HCl, HCOOH
- Base: proton acceptor: NH3, NaOH
- Acid-base reaction is a proton exchange reaction
• Conjugate acid and base:
- A conjugate base of an acid is the product after the acid
give out a proton
- A conjugate acid of a base is the product after the base
accepted a proton
- Example:
acid1 base1 + proton
conjugate base of acid
base2 + proton acid2
conjugate acid of base2
 Conjugate acid/base
• Neutralization reaction (a proton exchange reaction):
acid1 + base2 base1 + acid2

• Examples of conjugate acid-base pair

NH3 + H2O NH4+ + OH-
base1 acid2 conjugate conjugate
acid1 base2

H2O + HNO2 H3O+ + NO2-

base1 acid2 conjugate conjugate
acid1 base2
Acid and base
----Amphiprotic species
Amphiprotic species: species possess both acid and base
properties
Examples:
H2PO4- + H3O+ H3PO4 + H2O
base1 acid2 acid1 base2

H2PO4- + OH- HPO42- + H2O

acid1 base2 base1 acid2

NH2CH2COOH + H3O+ NH3+CH2COOH + H2O

base1 acid2 acid1 base2

NH2CH2COOH + OH- NH3CH2COO- + H2O

acid1 base2 base1 acid2

NH2CH2COOH NH3+CH2COO- (zwitterion)

base1 acid2 acid1 base2
 Amphiprotic solvent and autoprotolysis
• Amphiprotic solvent: a solvent acts either as an acid or as a base.
• Examples: H2O, NH3, HCOOH, CH3OH, C2H5OH.
• Autoprotolysis: a process solvents undergo self-ionization to
form a pair of ionic species.
• Examples
base1 acid2 acid1 base2
H2O + H2O H3O+ + OH-
NH3 + NH3 NH4+ + NH2-
CH3OH + CH3OH CH3OH2+ + CH3O-
HCOOH + HCOOH HCOOH2+ + HCOO-
 Chemical equilibrium

• Equilibrium state: the rate of reactants react to generate

products equals the rate of the products react to generate
reactants. (equilibrium, not static. No change macroscopically, but change microscopically)

• Expression:
reactant1 + reactant2 product1 + product2
• Equilibrium position is decided by the thermochemical
property of the reaction system, independent of the route
by which the equilibrium is reached (The 1st thermodynamic
law).
Equilibrium constant expression
• For a general chemical reaction:
wW + xX yY + zZ
• Equilibrium constant:
[Y]y[Z]z
K= (9-1)
[W]w[X]x
• [X] indicates the equilibrium concentration of component X.

• If a reactant is a pure liquid, pure solid or the solvent

present in excess, no term for that species appears in
the equilibrium constant expression.
[Y]y
K= (9-2) (Z is a solid reactant)
[W]w[X]x
 Type of equilibrium constants in
analytical chemistry
Type of Name&symbol Typical example Equilibrium
equilibrium of equilibrium constant
constant expression
Dissociation of Ion-product
water constant, Kw 2H2O H3O+ + OH- Kw = [H3O+][OH-]

Dissolving of Solubility
slightly soluble product, Ksp BaSO4(s) Ba2+ + SO42- Ksp = [Ba2+][SO42-]
substance

Dissociation of Dissociation
[H3O+][Ac-]
weak acid or constant, Ka or HAc + H2O H3O+ + Ac- Ka = [HAc]
base Kb

Complex Formation
[Ni(CN)42-]
formation constant, β Ni2+ + 4CN- Ni(CN)42- β = [Ni2+][CN-]4
 Type of equilibrium constants in
analytical chemistry
Type of Name&symbol Typical example Equilibrium
equilibrium of equilibrium constant
constant expression
Oxidation/reduction Kredox MnO4- + 5Fe2+ + 8H+ Kredox =
equilibrium Mn2+ + 5Fe3+ + 4H2O [Mn2+][Fe3+]5
[MnO4-][Fe2+]5[H+]8
Distribution of a
solute between Kd I2(aq) I2(org) Kd = [I2]org/[I2]aq
immiscible solvents
 Stepwise formation constant for
complexation reactions
• Stepwise formation of complexes
[Ni(CN)+]
Ni2+ + CN- Ni(CN)+ K1 =
[Ni2+][CN-]
[Ni(CN)2]
Ni(CN)+ + CN- Ni(CN)2 K2 =
[Ni(CN)+][CN-]

Ni(CN)2 + CN- NI(CN)3- [Ni(CN)3-]

K3 =
[Ni(CN)2][CN-]
Ni(CN)3- + CN- Ni(CN)42- [Ni(CN)42-]
K4 =
[Ni(CN)3-][CN-]
 Overall formation constant of
complexes
• Overall formation of complexes
[Ni(CN)2]
Ni2+ + 2CN- Ni(CN)2 β2 =K1 K2 =
[Ni2+][CN-]2
[Ni(CN)3]
Ni2+ + 3CN- Ni(CN)2 β3 =K1 K2 K3 =
[Ni2+][CN-]3
[Ni(CN)4]
Ni2+ + 4CN- NI(CN)4- β4 =K1 K2 K3 K4=
[Ni2+][CN-]4
 Application of equilibrium constant
in calculations
• “If a reactant is a pure liquid, pure solid or the solvent
present in excess, no term for that species appears in
the equilibrium constant expression”

Take water as an example: water molar concentration in an

dilute aqueous solution is:
1000g/L = 55.6 M
18 g
In a pure water solution, the dissociation reaction will generate 1.0 x 10-7
M H3O+ ions and 1.0 x 10-7 M OH- ions. If we add HCl to the solution to
make a 0.1 M HCl solution, Suppose all the OH- ions in water reacted with
H3O+ ions, then water concentration will increase 1.0 x 10-7 M. Therefore,
the change of water concentration is negligible.
 Q Do it your self
1. What is the H3O+ concentration in a 0.001 M
NaOH solution. (Kw = 1.00 x 10-14), and what is
the OH- concentration in the solution?
2. Suppose the Ksp for Ba(IO3)2 is 1.57 x 10-9.
What is the Ba2+ concentration and IO3-
concentration in a solution in equilibrium with
solid Ba(IO3)2 (a saturated Ba(IO3)2 solution).
3. if 2.00 x 10-2 M Ba2+ is added to the Ba(IO3)2
saturated solution, then, what is the
concentration of Ba2+ and IO3- in the solution.
(Common ion effect).
 Dissociation constants for
conjugate acid/base pair
• Take NH4+/NH3 conjugate acid/base pair as an example:
- Dissociation of NH4+ [NH3][H3O+]
NH4+ + H2O NH3 + H3O+ Ka =
[NH4+]
- Dissociation of NH3: [NH4+][OH-]
NH3 + H2O NH4+ + OH- Kb =
[NH3]

[NH3][H3O+] [NH4+][OH-]
KaKb = x = [H3O+][OH-] = Kw
[NH4+] [NH3]

Kw = KaKb (9-3)
 Q Do it yourself
• Calculate the dissociation constant of conjugate acid/base

Acid Ka Base Kb

NH4+ ? NH3 1.75 x 10-5

C6H5COOH 6.28 x 10-5 C6H5COO- ?

CH3COOH 1.75 x 10-5 CH3COO- ?

ClCH2COOH 1.36 x 10-3 ClCH2COO- ?

 Hydronium ion concentration of
solutions of weak acids
• Dissociation reactions in a weak acid solution
HA + H2O H3O+ + A- [A-][H3O+]
Ka = (9-4)
[HA]
2H2O H3O+ + OH- Kw = [H3O+][OH-]
• Water dissociation is negligible in such a solution
(common ion effect)

• Suppose the analytical concentration of the weak acid in the

solution is CHA
• What we need to know if we want to calculate [H3O+]
using the dissociation constant equation?
[A-][H3O+]
Ka = (9-4)
[HA]
 Hydronium ion concentration of
solutions of weak acids
[A-][H3O+]
• From the dissociation reaction: Ka =
[HA]
[A-] = [H3O+]
CHA = [A-] + [HA] = [H3O+] + [HA]
[HA] = CHA – [H3O+]
• Re-write dissociation constant expression:
[A-][H3O+] [H3O+]2
Ka = = (9-5)
[HA] CHA – [H3O+]
Resulted in an equation:
[H3O+]2 + Ka[H3O+] – KaCHA = 0 (9-6)
 Hydronium ion concentration of
solutions of weak acids
• Solution of equation (9-6):

-Ka + Ka2 + 4KaCHA

[H3O+] = (9-7)
2
• We are dealing with a WEAK acid, it is supposed the
dissociation is very limited. Therefore, we can assume
[H3O+] << CHA and CHA – [H3O+] = CHA

• Rewrite equation (9-5)

[H3O+]2
Ka = (9-8)
CHA

[H3O+] = KaCHA (9-9)

 Q Do it yourself
Acetic acid, CH3COOH, is an essential ingredient of
commercial vinegar, which gives the flavor you tasted. A
commercial vinegar usually have 5.00% (w/w) acetic acid.
The density of vinegar is 1.01 g/mL (http://www.apple-cider-vinegar-
benefits.com/properties-of-vinegar.html#phv). Suppose there is no
other ingredient contribute to [H3O+] in the vinegar, calculate
[H3O+] concentration in the vinegar (Acetic acid, MCH3COOH =
60.0 g; Ka = 1.75 x 10-5)
 Buffer solutions
• Definition: A buffer solution resist the changes in pH with
dilution or with addition of acid or base.
• Composition: buffer solutions consist of conjugate acid/base
pairs.
• Examples: NH3/NH4Cl, NaH2PO4/Na2HPO4, HOAc/NaOAc
Buffer solution calculation
-----What is the pH value of a buffer solution
• Dissociation reactions in a buffer solution consists of a
conjugate acid/base pair: HA/NaA
- +]
[A ][H O
HA + H2O H3O+ + A- Ka =
3 (9-4)
[HA]
A- + H2O HA + OH- [HA][OH-] Kw
Kb = = (9-10)
[A-] Ka
• From these reactions:
[HA] = CHA – [H3O+] + [OH-] = CHA (9-11)
[A-] = CNaA + [H3O+] - [OH-] = CNaA (9-12)

• Replace [HA] and [A-] in equation 9-4 with the value

expressed in equation 9-11 and 9-12
+ CHA (9-13)
[H3O ] = Ka
CNaA
pH = pKa - logCHA + logCNaA (9-14)
 Properties of buffer solutions
CHA
[H3O+] = Ka
CNaA
1. Buffer the pH change in dilution.
2. Buffer pH change in case acid or base of limited
quantity was added to the solution
• Example: a 400 mL buffer solution having 0.200 M
NH3 and 0.300 M NH4Cl. Calculate the pH change
after 100 mL of 0.0500 M NaOH solution is added to
the buffer solution. (NH3, Kb = 1.75 x 10-5)
Solution:
- Before addition of NaOH solution
pOH = pKb - logCNH3 + logCNH4Cl = 4.75 + 0.699 - 0.522
= 4.93
pH = 14.00 – 4.93 = 9.07
 Properties of buffer solution
• After adding NaOH solution
NH4+ + OH- NH3 + H2O
400x0.300 – 100x0.0500
CNH4+ = = 0.230 M
400 + 100
400x0.200 + 100x0.0500
CNH3 = = 0.170 M
400 + 100
pOH = pKb - logCNH3 + logCNH4Cl = 4.75 + 0.769 – 0.638
= 4.88
pH = 14.00 – 4.88 = 9.12
∆pH = 9.12 – 9.07 = 0.05

• If without buffer, the pH change will be from pH = 7 (pure

water) to pH = 12 (0.01 M NaOH). ∆pH = 5.
 The composition of buffer solutions
as a function of pH, α values
• α value: the relative equilibrium concentration of the two
components of a conjugate acid/base pair.
• A buffer solution consists of HA and NaA. The α values
for HA and NaA can be calculated with follow equation:
[H3O+]
αHA =
[H3O+] + Ka

[H3O+] + Ka
αNaA =
[H3O+]

In a solution with pH = pKa, αHA = αNaA. Most of the transition

between αHA and αNaA occurs within + 1 pH unit around pH =
pKa.
 Buffer capacity
• Definition: buffer capacity is the number of moles of a
strong acid or base that causes 1.00 L of a buffer solution to
undergoing a 1.00 unit change in pH.

dCb dCa
β=
dpH = - dpH

• The bigger the β value, the stronger the buffer solution to

resist a change of pH value caused by the addition of an
acid or base.
How to select and prepare a buffer solution

• Consider what pH range you want the

solution to keep, choose the central pH
value as close as possible to pKa
• Choose appropriate buffer capacity.
• The recipes of many commonly used
buffer solutions can be founded in
chemical handbooks (e.g. J. A. Dean, Analytical
chemistry Handbook, New York, McGraw-Hill, 1995).
 Q Question
• What is the components buffered the
potential vigorous pH change in river and
lake water caused by acid rain?