CHEM 2400/2480

Lecture 5

Review of Chemical Equilibrium

Reactions used in analytical chemistry are never complete. Instead,

they proceed to a state of chemical equilibrium in which the ratio of

concentrations of reactants and products is constant.

i.e. For the reaction:

aA + bB º cC + dD

the concentration equilibrium constant, K, is

[C]c [D]d
K =
[A]a [B]b

[ ] is the concentration of species relative to its standard state.

Standard state for solute = 1 M, gases = 1 atms

and solids and liquids = 1

Activity coefficient, γ , (chapter 8) will be omitted from calculations in

this course.

Week 3-1
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Basic Information required to follow Equilibrium

• Aqueous reactions involve H2O.

• Amphiprotic species behaves as an acid or a base depending on the

properties of the solute

e.g.

CH3COOH + H2O º CH3COO- + H3O+

Acid 1 Base 2 Base 1 Acid 2

and

NH3 + H2O º NH4+ + OH-

Base 1 Acid 2 Acid 1 Base 2

+ ve ion (cation) / acid ; - ve ion (anion) / base

• Autoprotolysis

- amphiprotic solvents undergo self ionization e.g.

CH3OH + CH3OH º CH3O- + CH3OH2+

2 H2O º H3O+ + OH-

[H 3 O + ] [OH −] + ] [OH −]
K = =[H O
[H 2 O]2 3

Note: in dilute solutions [H2O] = 55.6 M

Bronsted - Lowry Acids and Bases

Week 3-2
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Acids - proton donors

Bases - proton acceptors

pH = - log [H+]

pKw = pH + pOH = 14

neutral pH = 7

acid pH < 7

base pH > 7

Conjugate Acids and Bases

HA + B º A- + BH+
Acid 1 Base 2 Base 1 Acid 2

Acid Dissociation Constant

[H +] [A −]
HA º H +
+ A -
Ka =
[HA]

Base Hydrolysis Constant

[BH +] [OH −]
B + H2 O º BH+ + OH- Kb =
[B]

Week 3-3
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Relation Between Ka and Kb for a Conjugate pair

Ka Kb = Kw

[NH 4+] [OH −]

e.g. NH3 + H2O º NH4 + OH + -
Kb =
[NH 3 ]

[NH 3 ] [H 3 O +]
Ka =
NH4+ + H2O º NH3 + H3O+
[NH 4+]
______________________________________________

add: 2 H2O º H3O+ + OH- K w = [H 3 O +] [OH −]

______________________________________________

[NH 4+] [OH −]

= [H 3 O +] [OH −]
[NH 3 ] [H 3 O]
K aK b = x +
[NH 3 ] [NH 4 ]

∴ K a Kb = K w

Week 3-4
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SYSTEMATIC TREATMENT OF EQUILIBRIUM

Before we proceed, you must be comfortable with two new

concepts: ‘Mass Balance’ and ‘Charge Balance’

1. Mass Balance relates to the conservation of matter i.e.

• the relation of the equilibrium concentrations, [ ], of various

species in a solution to one another and to the analytical
concentration, C, of the various solute
• can have more than one mass balance equation
• misleading title because concentrations rather than masses are used

e.g. write the mass balance equations for a solution that is 0.050 M in
acetic acid (HAc)

In solution we have:

HAc + H2O º H3O+ + Ac-

2H2O º H3O+ + OH-

1st mass balance equation:

CHAc = 0.050 M = [HAc] + [Ac-]

2nd mass balance equation:

[H3O+] = [Ac-] + [OH-]

Week 3-5
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Write the mass balance equations for 0.10 M Na2CO3 solution

Na2CO3 º 2Na+ + CO32-

[Na +] 2
=
[CO 23−] 1

Week 3-6
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Write the mass balance for a saturated solution of Ag3PO4

Ag3PO4 º 3 Ag+ + PO43-

[Ag+] 3
ratio: =
[PO 43−] 1

Week 3-7
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Lecture 6

CHARGE BALANCE

An electrolyte solution is NEUTRAL and

the sum of the molar concentration of the +ve charges in solution

= the sum of the molar concentration of the -ve charges in

solution.

Note: There can only be ONE charge balance equation for a given
solution.

Contribution of charge by an ion

= molar concentration of that ion times its charge

e.g. Mg2+

mol +ve charge/L = mol Mg2+ x 2 mol +ve charge

L mol Mg2+

= 2 x [Mg2+]

Write the charge balance equation for MgCl2 with C MgCl2 = 0.100 M

2 [Mg2+] + [H3O+] = [Cl-] + [OH-]

2 (0.100) 1 x 10-7 2 (0.100) 1 x 10-7

For neutral solution [H3O+] and [OH-] are very small

ˆ 2 [Mg2+] = [Cl-] = 0.200 M

Week 3-8
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ACID - BASE EQUILIBRIA

Let’s consider weak acids and bases. We will deal with weak acids in
our lectures.

Weak Acid

HA + H2O º H3O+ + A- Ka

2 H 2 O º H3 O+ + OH- Kw

Mass balance:

CHA = [HA] + [A-]

Charge balance:

[H3O+] = [A-] + [OH-]

Week 3-9
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[H 3 O +] [A −]
Ka =
[HA]

but from massbalance

[HA] = C HA − [A −]

[H 3 O + ] [A −]
∴ =
C HA − [A −]
Ka

also from charge balance

[H 3 O +] = [A −] + [OH - ]

and [A −] = [H 3 O +] − [OH - ]

[H 3 O +] −
Kw
=
[H 3 O +]

⎧ ⎫
[H 3 O +] +
⎪ Kw ⎪
⎨ [H 3 O ] − ⎬
⎪
⎩ [H 3 O +] ⎪
⎭
∴ Ka =
⎧ K w ⎫⎪
C HA − ⎨ [H 3 O +] −
⎪
⎬
⎪
⎩ [H 3 O +] ⎪⎭

This is a cubic equation.

Week 3-10
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⎧ ⎫
[H O +] [
3
⎪
⎨
⎪
H 3O + −
Kw
] [
H 3O + ]
⎪
⎬
⎪
⎩ ⎭
Ka =
⎧ ⎫
C HA −
⎪
⎨
⎪
[H O +] − [HKO +]
3
w ⎪
⎬
⎪
⎩ 3 ⎭

− K H 3 O +⎤⎥ + K a K w = + 2
K a C HA ⎡ ⎡
H 3O ⎥ − K w
⎤
a⎢
⎣ ⎦ ⎡ +⎤ ⎢⎣ ⎦
⎢H 3 O ⎥
⎣ ⎦

⎛ ⎞
[H O +] [
+ K a H 3O + − ] ⎜ K aK w ⎟
2
+ K a C HA + ⎟ =0
3 ⎜K w
⎜
⎝ [ +
H 3 O ⎟⎠ ]

⎛ ⎞
⎜ K aK w ⎟
−K a + 2
+ + K +
[ ]
K 4⎜ K C HA ⎟
H 3O +
a w a
⎜ ⎟
[ ]
⎝ ⎠
H 3O + =
2

Week 3-11
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Use spreadsheet to solve this equation.

Excel uses ‘circular defintion’ Quattro uses ‘solve for’
Lecture 9
1. CONTRIBUTION from WATER

In real systems, one rarely has to worry about the contribution

of H+ or OH- from water. If you had a 10-8 M KOH solution,

you would have to protect it from the atmosphere to keep the

pH at the calculated value of 7.02.

Contributions from water are normally negligible. In this case:

[H 3 O +] >> [OH −] ≈
Kw
[H 3 O +]

∴ [H 3 O +] = [A −]

and

[H 3 O +] 2
Ka =
C HA − [H 3 O +]

This equation holds for:

- small and large concentration

- small and large Ka’s

Week 3-12
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But NOT extremes i.e.

- very small Ka’s and very small CHA

Week 3-13
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2. For the Extreme case of very little dissociation

⎧ K w ⎫⎪
C HA >>
⎪ +
⎨ [H 3 O ] − ⎬
⎪⎩ [H 3 O +] ⎪⎭

and

⎧ K w ⎫⎪
[H 3 O +] ⎨ [H 3 O +] −
⎪
⎬
⎪⎩ [H 3 O +] ⎪⎭
Ka =
C HA

∴ [H 3 O +] = K w + K a C HA

This equation holds for very small Ka’s

Week 3-14
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Relationship between pH, pKa and CHA

Analogy Between Weak Acid and Weak Base Equations

Week 3-15
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Weak acid Weak base

(1) [H+][A-] = Ka[HA] (1) [OH-][BH+] = Kb[B]

(2) [H+][OH-] = Kw (2) [OH-][H+] = Kw

(3) [H+] = [OH-] + [A-] (3) [OH-] = [H+] + [BH+]

(4) [HA] + [A-] = C (4) [B] + [BH+] = C

[H+] replaced by [OH-]

[OH-] replaced by [H+]

[HA] replaced by [B]

[A-] replaced by [BH+]

Ka replaced by Kb

Kw = Ka Kb

Week 3-16
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Also, salts of SB and WA: Species, Na+, A-

Kb: A- + H2O º OH- + HA

charge balance: [H+] + [Na+] = [A-] + [OH-]

mass balance: CNaA = [Na+]

CNaA = [A-] + [HA]

ˆ [H+] = [OH-] - [HA]

and, salts of WB and SA: species, BH+, Cl-

Ka: BH+ + H2O º B + H3O+

charge balance: [BH+] + [H+] = [OH-] + [Cl-]

mass balance: CBHCl = [Cl-]

CBHCl = [B] + [BH+]

ˆ [H+] = [OH-] + [B]

Week 3-17