Chapter 3

Aqueous Solutions and

Chemical Equilibria

1
 The chemical composition of aqueous solution
Water is used as medium or carrying out a chemical analysis because:
• the most plentiful solvent available on earth
• easily purified
• not toxic
• dissolved many substances
• serves as the medium in which a wide variety of chemical reactions take
place.
Most of the analytical processes we will discuss involves reactions in
aqueous solutions.
most solutes we discuss are electrolytes.
Electrolytes: it form ions when dissolved in water or certain other solvents
and produce solutions that conduct electricity.
The electrolytes can be classified according to their behavior when dissolved
in solvent in to:
2
1. Strong electrolytes: ionize essentially completely in a solvent.
2. weak electrolytes: ionize only partially.
Thus, a solution of a weak electrolyte will be a poorer conductor than a
solution containing an equal concentration of strong electrolyte.
Nonelectrolytes: Are substances that dissolve in water but do not produce any ions
and do not conduct an electric current.
The following table shows an example of electrolytes

Strong Weak
1. Inorganic acids such as HNO3, 1. Many inorganic acids, including
HClO4, H2SO4*, HCl, HI, HBr, H2CO3, H3BO3, H3PO4, H2S, H2SO3
HClO3, HBrO3 HF
2. Alkali and alkaline-earth 2. Most organic acids
hydroxides
3. Most salts ( ex. NaCl, 3. Ammonia and most organic bases
CH3COONa)
4. Halides, cyanides, and
thiocyanates of Hg, Zn, and Cd
* H2SO4 is a strong electrolyte, however, HSO4– is a weak electrolyte. 3
 Describing acids and bases
Acids: recognized as a class of substances that taste sour,
e.g. vinegar that contain acetic acid
Bases: (called alkalis) characterized by their bitter taste and slippery feel.

1)Arrhenius’ definition
The first person to recognize the essential nature of acids and bases was
Arrhenius. Arrhenius postulated that:
Acids: produce hydrogen ions in aqueous solution.
HA(aq) → H +(aq)+ A-(aq)
Bases: produce hydroxide ions when dissolved in water.
MOH(aq)→ M +(aq)+ OH -(aq)
Arrhenius concept of acids and bases is limited because:
• It applicable only to aqueous solutions.
• Allows for only one kind of base –the OH- ion.
4
• NH3 ammonia could not be an Arrhenius base.
2) Brönsted-Lowry definition:
In 1923, two chemists, BrǾnsted and Lowry proposed independently a theory
of acid/base behavior that is particularly useful in analytical chemistry.
According to BrǾnsted-Lowry theory:
An acid: is an proton (H+) donor
A base: is a proton acceptor.
Acids and bases always come in pairs. For a species to behave as an acid,
a proton acceptor (or a base) must be present. The reverse is also true.
It is apparent that not only molecules but also cations and anions may function
as acids and bases.
An important feature of the BrǾnsted-Lowry concept is the idea that:
The species produced when an acid gives up a proton is called conjugate
base of the parent acid (it is a proton acceptor)
e.g: acid1 base1 + proton
Acid1 and base1 are a conjugate acid/base pairs
Similarly, every base produces a conjugate acid as a result of accepting a
proton, that is: 5

base + proton acid

When these two processes are combined, the result is an acid /base, or
neutralization, reaction:
acid1 + base2 base1 + acid2
The extent to which this reaction proceeds depends on the relative tendencies
of the two bases to accept a proton, or the two acids to donate a proton.

Examples of conjugate acid/base relationships:

NH3 + H2O NH4+ + OH-

base1 acid2 conj. acid1 conj. base2

H2O + HNO2 H3O+ + NO2-

base1 acid2 conj. acid1 conj. Base2

Many solvents are proton donor or proton acceptor and can thus induce basic
or acidic behavior in a solutes dissolved in them.
From the previous examples:
water (H2O) can donate a proton to NH3 , and thus acts as an acid
water (H2O) can accept a proton from HNO2, and thus acts as a base and6
produce H O+ which is called hydronium ion H O+.
Chemists use the notation H3O+ or , more simply H+ when writing
chemical equations in which the proton is involved.
An acid that has donated a proton becomes a conjugate base capable of
accepting a proton to reform the original acid; the converse holds equally well.
For example: H2O + NO2- HNO2 + OH-

acid2 base1 conj. acid1 conj. Base2

This reaction is the one that causes an aq. solution of NaNO 2 to be slightly
basic.
Some species have both acidic and basic properties and called amphiprotic
solutes.
An example:
H2PO4- + H3O+ H3PO4 + H2O
base acid conj. acid conj. base
H2PO4- + OH- HPO4-2 + H2O
acid base conj. Base
+ conj. Acid
Amino acids are important class of amphiprotic compounds
For example: H2CH2COOH H3NCH2COO-
7
They undergo a kind of internal acid-base reaction to produce a zwitterion (an
Amphiprotic Solvents:
It is a solvent that can act either as an acid or as a base depending on the
solute. Water is the classic example.
Other common amphiprotic solvents are CH3OH, C2H5OH, NH3, CH3COOH
For example: NH3 + CH3OH NH4+ + CH3O-
base1 acid2 conj. acid1 conj. base2

HNO2 + CH3OH NO2- + CH3OH2+

acid2 base1 conj. base2 conj. acid1
Solvents and Autoprotolysis
Amphiprotic solvents undergo self-ionization, or autoprotolysis, to form a
pair of ionic species. Autoprotolysis is another example of acid/base behavior,
as
illustrated by the following equations
base1 + acid2 acid1 + base2
H2O + H2O H3O+ + OH-
8
CH3OH + CH3OH CH3OH2+ + CH3O-
Strong and weak acids and bases
The following table shoes the dissociation reaction of a few common acids in
water.
From the table, you can note that:
 the acids become weaker from top to bottom. The first two are strong acids
(HCl, HClO4) because they dissociate completely in water, no undissociated

solute molecules remain.

Relative Strength of some common acids and their conjugate bases 9

The other weak acids, which react incompletely with water to give solutions
that contain significant amounts of both the parent acid and its conjugate
base. For example; acetic acid (HC2H3O2) is 1%dissociate,
ammonium ion (NH4+) weaker acid; 0.01%dissociate.
 the weakest acid form the strongest conjugate base; NH 3 has a much
stronger affinity to proton than any base above it.
ClO4-, Cl- have no affinity for protons in aqueous solution.
Acid and base strengths that are not distinguished in aqueous solution may be
distinguishable in non-aqueous solvents.
The tendency of a non-aqueous solvents to accept or donate protons
determines the strength of the acid or base dissolved in it. HCl, HClO 4 are
strong acids in water, if unhydrous CH3COOH is used as solvent instead of
water, neither of these acids undergoes complete dissociation; instead,
equilibria such as the following are established:
HClO4 + CH3COOH ClO4– + CH3COOH2+ K = 1.3×10–5
strong acid base weak base weak acid
HCl + CH3COOH Cl– + CH3COOH2+ K = 5.8×10
10
–8
HClO4 is stronger acid than HCl in CH3COOH solvent; its dissociation is
about 5000 times greater. CH3COOH thus acts as differentiating solvent
toward the two acids.
In a differentiating solvent, various acids dissociate to different degrees and
have different strengths.
Water, on the other hand, is a leveling solvent for several strong acids
(like HCl, HClO4, HNO3) which are completely dissociated and show the
same strength.

11
 Chemical Equilibrium
• Most of the chemical reactions never result in complete conversion of
reactants to products. They proceed to a state of chemical equilibrium in
which the ratio of concentrations of reactants and products is constant.
• Equilibrium-constant expressions are algebraic equations that describe the
concentration relationships that exist among reactants and products at
equilibrium.
• Among other things, equilibrium-constant expression permit us to calculate
the error that result from any unreacted analytes remaining when
equilibrium has been reached.
• Consider the following chemical equilibrium:
H3AsO4 + 3 KI + 2 H+ H3AsO3 + I3- + H2O
 If 1 mmol of H3AsO4 added to 100 mL of a solution containing 3 mmol of KI,
the red color of I3- appears almost immediately and within a few seconds the
intensity of the color become constant; I3- concentration has become constant.
 If 1 mmol of H3AsO3 added to 100 mL of a solution containing 1 mmol of I 3- ,
the color intensity greater than the first solution but rapidly decrease to reach the
intensity of the first solution. 12
• Many other combinations of the four reactants can be used to yield
solutions of the same intensity, so the position of a chemical equilibrium is
independent of the route by which equilibrium is reached. This relationship
is altered by the application of stress of the system.
• Such stresses include changes in temperature, pressure, total concentration
of reactant or product. These effects can be predicted qualitatively from the
principle of Le-Chatelier.
• The Le-Chatelier principle states that the position of an equilibrium always
shifts in such a direction as to relieve a stress that is applied to the system.
• An equilibrium shift brought about by changing the amount of one of the
participating species is called the mass-action effect.

Writing Equilibrium Constants

The influence of concentration (or pressure for gaseous species) on the position
of a chemical equilibrium is described quantitatively by means of an
equilibrium-constant expression.
Equilibrium-constant expression provides no information as to whether a
chemical reaction is fast enough to be useful in an analytical procedure.
13
Let us consider the general chemical reaction:
wW + xX yY + zZ

Where, the capital letters represent the formulas of participating chemical

species and the lowercase letters are the small whole numbers (# of moles)
required to balance the equation. The equilibrium-constant expression is
[Y]y [Z]z
K=
[W]w [X]x
Where, the bracketed terms are molar concentration if the species is a
dissolved solute or partial pressure (atm) if the species is a gas. If one of the
species is a pure liquid, a pure solid, or the solvent in excess (dilute soln.), no
term for this species appear in the equilibrium-constant expression.
Equilibrium constant K is a temperature dependent quantity.

14
Important Equilibrium Constants in Analytical Chemistry
The following table summarize the types of chemical equilibria and
equilibrium constants that are importance in analytical chemistry.

Type of equilibrium Name and symbol of Typical example Equilibrium-constant

equilibrium constant expression
Dissociation of water Ion-product constant, 2H2O Kw = [H3O+] [OH-]
Kw H3O+ + OH-
Equilibrium of Solubility product BaSO4 Ksp = [Ba+2] [SO4-2]
slightly soluble salt Constant, Ksp Ba+2 + SO4-2
[NO2-] [H3O+]
Dissociation of a Acid or base HNO2 +H2O Ka =
weak acid or base dissociation constant, NO2- +H3O+ [HNO2 ]
Ka ,Kb NH3 +H2O [NH4+][OH-]
Kb =
NH4+ + OH- [NH3 ]
[Ni(CN)4-2]
Formation of ,Formation constant Ni+2 + 4 CN- Kβ =
[Ni+2] [CN-]4
complex ion βn Ni(CN)4-2
Simple applications of some of these constants are illustrated in the
paragraphs that follow 15
1) The Ion-Product Constant for Water (Kw)
Aqueous solutions contain small concentrations of hydronium and hydroxide
ions as a consequence of the dissociation reaction.
2 H2O H3O+ + OH-
Equilibrium constants,
[H3O+] [OH-]
K=
[H2O ]2
The concentration of water in dilute aqueous solution is enormous when
compared with the concentration of hydrogen and hydroxide ions. [H 2O] can
be taken as constant,
K[H2O]2 = Kw = [H3O+][OH-]
where the new constant is the ion-product constant for water. At 25 oC,
Kw 1.00 x 10-14
-logKw = - log[H3O]+ - log[OH-]
pKw = pH + pOH = 14.00

16
Example: Calculate the hydronium and hydroxide ion concentrations of
pure water at 25°C and 100°C (Kw= 49 X 10-14 M).
2 H2O H3O+ + OH-
[H3O+] = [OH-] substitution into: Kw = [H3O+][OH-]

Kw = [H3O+]2 = [OH-]2 √ Kw = [H3O+] = [OH-]

√1.00 x 10-14 = [H3O+] = [OH-] = 1.00 x 10-7 M
At 100°C, [H3O+] = [OH-] = √ 49 X 10-14 = 7 x10-7 M
Example: Calculate the hydronium and hydroxide ion concentrations in
0.200 M aqueous NaOH.
NaOH is a strong base, so it dissociate completely in water, so [NaOH] =[OH-]
[OH-]totat = [NaOH] + [OH-]dissoc. of water
[OH-] from the water is insignificant (very small compared with 0.2 M )
[OH K 1 x 10 -14
[H3O] ]≈=0.200 wM =
-+
= 5.00 x 10-14
[OH-] 0.200 17
2) Solubility-Products constants (Ksp)
Most sparingly soluble salts are essentially completely dissociate in saturated aqueous
solution (completely dissociate, do not imply that all the salt
dissolves; very small amount that does go into solution dissociate completely).
for example when Ba(IO3)2 is equilibrated with water, the dissociation process is described
by the process

Ba(IO3)2(s) Ba2+(aq) + 2IO3-(aq)

[Ba2+][IO3-]2
K=
[Ba(IO
The [Ba(IO3)2] is however constant no3)matter
2] how much excess solid present

Therefore: K [Ba(IO3)2(s)] = Ksp = [Ba2+][IO3-]2

Where, the new constant, Ksp, is called the solubility-product constant.
The position of this equilibrium is independent of the amount of Ba(IO3)2 as
long as some solid is present; that is, it does not matter whether the amount is a few milligram
or several grams.
In general: for a sparingly soluble salts MpXq, Ksp = [M]p [X]q

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Solubility-Product Constants (Ksp) of Selected Ionic Compounds at 250C

Name, Formula Ksp

Aluminum hydroxide, Al(OH)3 3 x 10-34

Cobalt (II) carbonate, CoCO3 1.0 x 10-10
Iron (II) hydroxide, Fe(OH)2 4.1 x 10-15
Lead (II) fluoride, PbF2 3.6 x 10-8
Lead (II) sulfate, PbSO4 1.6 x 10-8
Mercury (I) iodide, Hg2I2 4.7 x 10-29
Silver sulfide, Ag 2S 8 x 10-48
Zinc iodate, Zn(IO3)2 3.9 x 10-6
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Example: Write the ion-product expression for each of the following
(a) Magnesium carbonate (b) Iron (II)hydroxide
(c) Calcium phosphate
Write an equation which describes a saturated solution.

(a) MgCO3(s) Mg+2 (aq) + CO3-2 (aq) Ksp = [Mg+2][CO3-2]

(b) Fe(OH)2(s) Fe+2 (aq) + 2OH-(aq) Ksp = [Fe2+][OH-]2

(c) Ca3(PO4)2(s) 3Ca+2 (aq) + 2PO4-3 (aq) Ksp = [Ca2+]3[PO43-]2

20
The solubility-product expression permits the ready calculation of the
solubility of sparingly soluble substance that ionized.

Example: Calculate the solubility of Ba(IO3)2 (molar mass = 487 g/mol) in

water in (mol/L) and (g/L), for Ba(IO3)2 Ksp = 1.57 x 10-9
Ba(IO3)2(s) Ba2+(aq) + 2IO3-(aq)
Ksp = [Ba2+][IO3-]2 = 1.57 x 10-9
The equation describing the equilibrium reveals that:
each 1.0 mol Ba(IO3)2 that dissolved = 1.0 mol Ba2+ formed = 2.0 mol IO3- formed
Molar solubility Ba(IO3)2 = [IO3-]
[IO3-] = 2 [Ba2+]
Substituting this last equation into the equilibrium-constant expression
[Ba2+] (2 [Ba2+])2 = 4 [Ba2+]3 = 1.57 x 10-9
1/3
[Ba2+] = 1.57 x 10 -9
= 7.32 x 10-4 M = solubility
4

Solubility ofBa(IO ) in g/L = 7.32 x 10-4 (mol/L) x 487 (g/mol) = 0.356 g 21

Example: Calculate Ksp for CuBr (molar mass 143.5 g/mol) if its solubility
of 0.0287 g/L at 25 C.
CuBr(s) Cu+(aq) + Br -(aq)
Ksp = [Cu+] [Br -]
0.0287 g/L
Solubility of CuBr (mol/L) = = 2.0 x 10-4 mol/L = [Cu+] = [Br -]
143.5 g/mol

Ksp = [Cu+] [Br -] = (2.0 x 10-4 mol/L)2 = 4 x 10-8

22
 Table : Relationship Between Ksp and Solubility at 250C

No. of Ions Formula Cation:Anion Ksp Solubility (M)

2 BaCO3 1:1 5.0 x 10-9 7.1 x 10-5

2 FeCO3 1:1 2.1 x 10-11 4.6 x 10-6
2 AgSCN 1:1 1.1 x 10-12 1.0 x 10-6
2 PbCrO4 1:1 3.0 x 10-13 5.5 x 10-7

3 Ba(IO3)2 1:2 1.57 x 10-9 7.3 x 10-4

3 CaF2 1:2 3.2 x 10-11 2.0 x 10-4
3 Ag2CrO4 2:1 2.6 x 10-12 8.7 x 10-5
3 Mn(OH)2 1:2 2.0 x 10-13 3.7 x 10-5

23
Predicting formation of precipitate:
A simple use of the solubility product constant is to predict whether or not a
precipitate of a salt will form when two given solutions are mixed. To do this
we calculate the reaction quotient, Q, from the ion concentrations. Recall Q
has the same form as the Ksp expression except that actual concentration and
not equilibrium concentrations are used to calculate its value.
In this case we refer to Q as the ionic product and we compare the value of Q
with the values of the Ksp for the particular salts. There are three possibilities:
a) If Q < the Ksp, then the solution is unsaturated and no precipitate will
form.b) If Q = Ksp, the solution is just saturated.
c) If Q > Ksp, then the solution is supersaturated and a precipitate will form
until the ionic product becomes equal to the K sp.

24
Example: We mix 2.3 x 10-4 M CaCl2 solution with 8.8 x 10-2 M Na2CO3.
Will a precipitate form. (for CaCO3 Ksp = 5.0 x 10-9)
CaCO3(s) Ca+2(aq) + CO3-2(aq)
we calculate at this time the reaction quotient, Q
QKsp = [Ca+2] [CO3-2]
QKsp = (2.3 x 10-4) (8.8 x 10-2) = 2.024 x 10-5
Now we compare the QKsp with the real value for Ksp :
QKsp (2.024 x 10-5) > Ksp (5.0 x 10-9)
then the solution is supersaturated and a precipitate will form until the ionic
product becomes equal to the Ksp.
Example: what CrO4-2 concentration is required to initiate the
precipitation of Ag2CO4 from a solution that contain 2.12 x 10-3 M Ag+.
(for Ag2CrO4 Ksp = 1.2 x 10-12)
K 1.2 x 10 -12
= 2.67 x+ 10
2 -7 M -2
Ag[CrO
CrO4(s)] =
-2 2spAg+
= + CrO -2
K = [Ag ] [CrO4 ] = 1.2 x 10-12
[Ag+]2 (2.12 x 10 )
2 (aq) 4 (aq)
-3 2 sp
4
25
[CrO4-2] > 2.67 x 10-7 M to initiate the precipitation
How does a Common Ion Affect the solubility of a precipitate:
The common ion effect is responsible for the reduction in solubility of an
ionic precipitate when a soluble compound combining one of the ions of the
precipitate is added to the solution in equilibrium with the precipitate. It states
that if the concentration of any one of the ions is increased, then, according
to Le Chatelier’s principle, the ions in excess should combine with the
oppositely charged ions. Some of the salt will be precipitated until the ionic
product is
equal to the solubility product constant. In simple words, common ion effect is
defined as the suppression of the degree of dissociation of a weak electrolyte
containing a common ion.
adding
AgCl  Ag +(aq)
(s) → NaCl( + 
Cl -      
aq ) shifts
(aq) equilibrium position

26
Example: calculate the molar solubility of Ba(IO3)2 in a solution that is
0.0200 M in Ba(NO3)2 .
Ba(IO3)2(s) Ba2+(aq) + 2IO3-(aq)
Ksp = [Ba2+][IO3-]2 = 1.57 x 10-9
Ba(NO3)2 is completely dissociate in water, so [Ba+2] = [Ba(NO3)2]
[Ba+2]total = [Ba+2]from Ba(NO3)2 + [Ba+2] from the dissociation of Ba(IO3)2
[Ba+2]total = [Ba(NO3)2]+ x
[Ba+2] from the dissociation of Ba(IO3)2 << [Ba+2] from Ba(NO3)2
Then, [Ba+2]total = [Ba+2]from Ba(NO3)2
[IO3-] = 2 x (from the dissociation of Ba(IO3)2)
Ksp = [Ba2+][IO3-]2 = 1.57 x 10-9 = (0.02) (2x)2 = (0.02) (4 x2) = 0.08 x2
x2 = (1.57 x 10-9 / 0.08) = 1.96 x 10-8
x = 1.4 x 10-4 M
Compare this solubility with the solubility in pure water (7.32 x 10 -4 M )??
Presence of a common ion decreases solubility of a slightly soluble ionic 27
compound.
Example: The Ksp for Ce(IO3)3 is 3.2 x 10-10. what is [Ce+3] and [IO3-] in
a solution prepared by mixing 50.0 mL of 0.05 M Ce+3 with 50.0 mL of:
a) Water b) 0.05 M IO3- c) 0.15 M IO3- d) 0.3 M IO3-
Ce+3 + 3 IO3- Ce(IO3)3
a) No reaction, only a dilution for Ce+3 solution will occur
(M V)conc. = (M V)diluted
0.05 M x 50.0mL = M x 100.0 mL M Ce+3 = 0.025 M
b) mmol Ce+3 = 0.05 M x 50.0 mL = 2.5 mmol/1
L.R. is IO3-
mmol IO3- = 0.05 M x 50.0 mL = 2.5 mmol/3
1 mol Ce +3
moles of Ce+3 reacted = moles of IO3- x = (2.5/3) = 0.83 mmol
3 mol IO3-
Excess moles of Ce+3 = [Ce+3]total - [Ce+3]reacted = 2.5 – 0.83 = 1.167 mmol
[Ce+3]unreacted = (1.167 mmol/100 mL) = 0.0117 M
Ignore it, very small
[Ce+3]total = [Ce+3]unreacted + [Ce+3]dissociation of Ce(IO3)3 compared with
[IO3-]= from the dissociation of Ce(IO3)3 only [Ce+3]unreacted
Ksp = [IO3-]3 [Ce+3] 3.2 x 10-10 = (3 x)3 (0.0117) = 0.32 x3 x= 1x10-3
- -3 -3
28
c) mmol Ce+3 = 0.05 M x 50.0 mL = 2.5 mmol/1 Stoichiometric
mmol IO3- = 0.15 M x 50.0 mL = 7.5 mmol/3 amounts, no L.R.
[Ce+3] and [IO3-] only from the dissociation of the precipitate, Ce(IO3)3.
Ksp = [IO3-]3 [Ce+3]
3.2 x 10-10 = (3 x)3 (x) = 27 x4 x = 2.28 x 10-4 M
[IO3-] = 3 x 2.28 x 10-4 = 6.84 x 10-4 M [Ce+3] = 2.28 x 10-4 M

d) ) mmol Ce+3 = 0.05 M x 50.0 mL = 2.5 mmol/1

L.R. is Ce+3
mmol IO3- = 0.30 M x 50.0 mL = 15 mmol/3
3 mol IO3-
moles of IO reacted = moles of Ce x
3
- +3
= (2.5 x 3) = 7.5 mmol
1 mol Ce +3

Excess moles of IO3- = [IO3-]total - [IO3-]reacted = 15 – 7.5 = 7.5 mmol

[IO3-]unreacted = (7.5 mmol/100 mL) = 0.075 M
Ignore it, very small
[IO3 ]total = [IO3 ]unreacted + [IO3 ]dissociation of Ce(IO3)3
- - -
compared with
[Ce+3] = from the dissociation of Ce(IO3)3 only [IO3-]unreacted
Ksp = [IO3-]3 [Ce+3] 3.2 x 10-10 = (0.075)3 (x) x= [Ce+3] =7.6x10-7M
29
3) Dissociation Constants for Acids and Bases
When a weak acid or base is dissolved in water, partial dissociation occur.
For HNO2 (weak acid), we can write:
HNO2 + H2O(ℓ) H3O+ + NO2-
Ka: is the acid dissociation constant.
For NH3 (weak base), we can write:
NH3 + H2O(ℓ) NH4+ + OH-
Kb: is the base dissociation constant.
Note [H2O] does not appear in the dissociation constant because
[H2O] >> relative to [acid or base] that the dissociation does not alter [H 2O]
Appreciably.
The values of Ka, Kb are found in your text book

30
Dissociation Constants for conjugate Acids /Bases pairs
For NH3 (weak base), we can write:
NH3 + H2O(ℓ) NH4+ + OH-
The dissociation of NH4+ (conjugate acid):
NH4+ + H2O(ℓ) NH3 + H3O+
Multiplication of one equilibrium-constant expression by the other gives:
[H3O+][NH3 ] [OH-][NH4+]
Ka Kb = x = [H O +
] [OH -
]
[NH4+] [NH3] 3

Kw =[H3O+] [OH-]
Kw = Ka Kb
Example: what is Kb for the following equilibrium:
CN- + H2O HCN + OH-
Given that : Ka for HCN = 6.2 x 10-10 1.0 x 10-14
Kb = [HCN][OH
-
] Kw = = 1.61 x 10 -5
= 6.2 x 10-10
[CN-] Ka 31
Calculating the [H3O+] concentrations in solutions of weak acids:
When HA (weak acid) dissolved in H2O, two equilibria are established:

HA + H2O(ℓ) H3O+ + A-

2 H2O H3O+ + OH- Kw =[H3O+][OH-]

[H3O+] produced from HA suppress the dissociation of H 2O to such an extent that the
contribution of H3O+ from water is negligible. negligible
[H3O+]total = [H3O+] from dissociation of HA + [H3O+] from H2O
[H3O+] ≈ [A-]
Also the sum of the molar concentration of HA and its conjugate base must be equal to
the analytical concentration of the acid.
CHA = [A-]dissoc. + [HA]undissoc.
Or CHA = [H3O+] + [HA] [HA] = CHA - [H3O+]
Substitute these values in Ka :

[H3O+]2 + Ka[H3O+] - KaCHA = 0

The positive solution to this quadratic equation is: 32
 -K + √K 2
a + 4Ka CHA
[H3O ] =
+ a
2
We can find the [H3O ] by making additional assumption: dissociation of the
+

weak acid does not appreciably decrease the molar concentration of HA.
Thus: [H3O+] << CHA , CHA - [H3O+] ≈ CHA

So:

[H3O+] = √ Ka CHA
The magnitude of error introduced by this assumption ([H3O+] << CHA ) increase as:
• The CHA become smaller.
• Ka become larger.
The following table show the effect of these two factors.
Notes:
• the error introduced by the assumption is about 0.5% when CHA/Ka = 104.
• The error increases to about 1.6% when CHA/Ka = 103.
• The error increases to about 5% when CHA/Ka = 102. 33
• The error increases to about 17% when C /K = 10.
 Errors introduce by the assumption that [H3O+] << CHA
Ka CHA using ]+H3O[ CHA using ]+H3O[ error%
assumption Ka .Quadratic equa

x 10-2 1.00 x 10-3 1.00 x 10-3 3.16 0.1 x 10-3 0.92 244
x 10-2 1.00 x 10-2 1.00 1.0 x 10-2 0.62 61
x 10-1 1.00 x 10-2 3.16 10 x 10-2 2.7 17
x 10-4 1.00 x 10-4 1.00 x 10-4 1.00 1 x 10-4 0.62 61
x 10-3 1.00 x 10-4 3.16 10 x 10-4 2.7 17
x 10-2 1.00 x 10-3 1.00 102 x 10-3 0.95 5.3
x 10-1 1.00 x 10-3 3.16 103 x 10-3 3.11 1.6
x 10-6 1.00 x 10-5 1.00 x 10-6 3.16 10 x 10-6 2.7 17
x 10-4 1.00 x 10-5 1.00 102 x 10-5 0.95 5.3
x 10-3 1.00 x 10-5 3.16 103 x 10-5 3.11 1.6
x 10-2 1.00 x 10-4 1.00 104 x 10-5 9.95 0.5
x 10-1 1.00 x 10-4 3.16 105 x 10-4 3.16 0.0
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Example: calculate the [H3O+] and [OH-] for each the following:
a) 0.020 M HClO, Ka = 3.0 x 10-8
b) 0.010 M ClCH2COOH Ka = 1.36 x 10-3
a) HClO + H2O(ℓ) H3O+ + ClO-
[H3O+] = [ClO-] [HClO] = 0.02 - [H3O+]
Introduce these relationship in Ka.
Assume [H3O+] << 0.02

[H3O+] = √ 0.02 x 3.0 x 10-8

= 2.4495 x 10-5

[H3O+] from2.44799
solving xthe quadratic equation
10 - 2.4495 x 10
-5 -5 = 2.44799 x 10 -5

x100% = 0.06%
2.44799 x 10-5
%error =
So the assumption is valid

35
b) ClCH2COOH + H2O(ℓ) H3O+ + ClCH2COO-

CHA 0.01
= = 7.35 %error that will be introduce is
Ka 1.36 x 10 -3
≈17%
So, we can not use the assumption to calculate [H 3O+], we must use the
quadratic equation to xcalculate
-1.36 10 -3
+ √ [H O+]x 10-3)2 + 4x1.36 x 10-3 x0.01.
(1.36
3
[H3O+] =
2

[H3O+] = 3.07 x 10-3 M [H3O+] = √ 0.01 x 1.36 x 10-3

= 3.688 x 10-3 M
If we assume that [H-33O ] << CHA -3
+
3.07 x 10 - 3.688 x 10 x100% = 20.1%
3.07 x 10-3
%error =

36
Calculating the [H3O+] concentrations in solutions of weak bases:
The techniques used to calculate [H3O+] for weak acids are readily adopted for
weak bases.
Example: calculate [H3O+] concentration of 0.075 M of NH3 solution
NH3 + H2O(ℓ) NH4+ + OH-

Cbase
= 4.3 x 103
the ratio of Kb
So the [NH4+] = [OH-] and [NH3] = [CNH3]
[OH-] = √ Kb Cbase
Rearrange Kb: then

[OH-] = 1.15 x 10-3 M

The source of H3O+ is only from the dissociation o water, then:
[H3O+] = (Kw/ [OH-]) = 1.0 x 10-14/ 1.15 x 10-3 ) = 8.696 x 10-12 M
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Example: calculate [H3O+] concentration of 0.015 M of sodium
Hypochlorite (NaClO) solution. (Ka for HClO = 3.0 X 10-8)
OCl-+ H2O(ℓ) HClO + OH-

1.0 x 10-14 = 3.33 x 10-7

=
3.0 x 10-8
Cbase
the ratio of = 4.5 x 104
Kb
[OH-] = √ Kb Cbase

[OH-] = 7.07 x 10-5 M

The source of H3O+ is only from the dissociation o water, then:
[H3O+] = (Kw/ [OH-]) = 1.0 x 10-14/ 7.07 x 10-5 ) = 1.415 x 10-10 M

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