CHE 401 : ANALYTICAL CHEMISTRY

MODULE
3
CHEMICAL EQUILIBRIA OF AQUEOUS SOLUTIONS

INTRODUCTION
This module provides a fundamental approach to chemical equilibrium, including calculations of
chemical composition and of equilibrium concentrations for monoprotic acid/base systems. Buffer
solutions and its properties, which are extremely important in many areas of science, are also
discussed. The students will be given an introduction on the effect of electrolytes on aqueous
solutions.

INTENDED LEARNING OUTCOMES

At the end of the module, the following learning outcomes are expected to be acquired by the
students:
1. Understand the concepts and be familiar with the steps and techniques employed in
gravimetric and volumetric method of analysis.
2. Execute calculation techniques used in stoichiometric analysis.
3. Acquire skills in laboratory technique required to perform and plan chemical analysis and
systematically collect and interpret data obtained in quantitative analytical process

CONTENT OVERVIEW
Indicative contents included the following topics:
1. Aqueous solutions and chemical equilibria
2. Buffer solutions
3. Effect of electrolytes on chemical equilibria
4. Solving equilibrium problems for complex systems

END OF THE MODULE TEST

The following are the assessment provided to evaluate students level of understanding after the
discussion of the modules:

Coursework (10 points )

Solving problems involving chemical equilibria, buffer solution, effect of electrolytes and
complex systems

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CHE 401 : ANALYTICAL CHEMISTRY

Table of Contents

MODULE 3. CHEMICAL EQUILIBRIA OF AQUEOUS SOLUTION ............................... 3

3.1 AQUEOUS SOLUTIONS AND CHEMICAL EQUILIBRIA ........................................ 3
3.1.1 Classification of electrolytes ..................................................................................... 3
3.1.2 Acids and Bases ........................................................................................................ 4
3.1.3 Chemical Equilibrium ............................................................................................... 7
3.1.4 Equilibrium constant equation .................................................................................. 9
3.1.5 Solubility Product Constant .................................................................................... 12
3.1.6 Acid-Base Dissociation Constant ........................................................................... 15
3.2 BUFFER SOLUTION .................................................................................................... 19
3.2.1 The Henderson-Hasselbalch Equation .................................................................... 19
3.2.2 Properties of Buffer Solutions ................................................................................ 20
3.3.3 Weak Acid – Base ionization.................................................................................. 22
3.3 EFFECT OF ELECTROLYTES IN CHEMICAL EQUILIBRIA ................................. 23
3.3.1 The Effect of Ionic Strength ................................................................................... 23
3.3.2 Activity Coefficients ............................................................................................... 25
3.3.2 The Debye-Huckel Equation................................................................................... 27
3.4 END OF MODULE TEST ............................................................................................. 29

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MODULE 3. CHEMICAL EQUILIBRIA OF AQUEOUS SOLUTION

3.1 AQUEOUS SOLUTIONS AND CHEMICAL EQUILIBRIA

An aqueous solution is a solution in which the solvent is water. Water is widespread use as medium
in carrying out chemical analysis. An aqueous solution is shown in Fig 1.3 in which the solute is
NaOH and solvent is water.

Fig. 3.1 Aqueous solution of NaOH

In this module, the solute which will be discuss further are electrolytes. Solution of electrolytes are those
which forms ions when dissolved in solvent hence produce solutions that conduct electricity.

3.1.1 Classification of electrolytes

Electrolytes are classified as strong and weak. Strong electrolytes completely ionize in a solvent while the
weak electrolytes partially ionize. Weak electrolytes will not conduct electricity and solutions containing
equal concentration of strong electrolytes. Figure 3.2 shows the effect of ions on the electrical conductivity
of water.

(a) (b) (c)

Fig. 3.2 Aqueous solution of NaOH

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Pure water Fig 3.2 (a) or an aqueous solution of a nonelectrolyte allows almost no current to flow,
and the bulb does not light. A weak electrolyte Fig 3.2 (b) produces a few ions, allowing some
current to flow and the bulb to glow dimly. A strong electrolyte Fig 3.2 (c) produces many ions,
allowing more current to flow and the bulb to shine brightly.

Solutes that forms strong and weak electrolytes are presented in Table 3.1.

Table 3.1 Classification of electrolytes

Strong Weak

1. Inorganic acids such as HNO3, HClO4, 1. Many inorganic acids. Including H2CO3,
H2SO4, HCl, HI. HBr, HCIO3, HBrO3 H3BO3, H3PO4,H2S, H2SO3

2. Alkali and alkaline-earth hydroxides 2. Most organic acids

3. Most salts 3. Ammonia and most organic bases

4. Halides, cyanides and thiocyanates of Hg,

Zn. and Cd
Note : H2SO4 is completely dissociated into HSO4 and H3O+ ions and for this reason is classified as a strong
electrolyte. It should be noted however that the HSO4- ion is a weak electrolyte. Being only partially dissociated
into SO4 and H3O+.

H2SO4 → HSO4- + H3O+ strong electrolyte

HSO4- ↔ SO42- + H+ weak electrolyte

3.1.2 Acids and Bases

J. N. Bronsted in Denmark and J. M. Lowry in England proposed independently a theory of
acid/base behavior that is particularly useful in analytical chemistry in 1923. According to this
theory :

An acid is a proton donor while the base is a proton acceptor.

H+ + OH- ↔ H2O (3.1)

Acid Base

The hydronium ion (H+) donate 1 proton, hence behave as an acid. On the other way, the hydroxide
ion (OH-) accepts a proton, thus so called a base.

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Conjugate Acids and Bases

An important feature of the Bronsted-Lowry concept is the idea that the product formed when an
acid gives up a proton is a potential proton acceptor and is called the conjugate base of the parent
acid.
acid1↔ base1 + proton (3.2)
base2 + proton ↔ acid2 (3.3)

Conjugate acid-base pair

acid1 and base1
base2 and acid2

When these two processes are combined, the result is an acid/base, or neutralization reaction.

acid1 + base2 ↔ base1 + acid2 (3.4)

Many solvents are proton donors or proton acceptors and can thus induce basic or acidic behavior
in solutes dissolved in them.

Examples :

1. Aqueous solution of ammonia water can donate a proton and thus acts as an acid with
respect to the solute:

NH3 + H2O ↔ NH4+ + OH- (3.5)

base1 acid2 conjugate conjugate
acid1 base2

In this reaction, ammonia (base) reacts with water which is labelled acid, to give the conjugate
acid ammonium ion (acid) and hydroxide ion which is the conjugate base (base) of the acid
water.

2. In an aqueous solution of nitrous acid, water acts as a proton acceptor or base

H2O + HNO2 ↔ H3O+ + NO2- (3.6)

base1 acid2 conjugate conjugate
acid1 base2

An acid that has donated a proton becomes a conjugate base capable of accepting a proton to re-
form the original acid; the converse holds equally well. Thus, nitrite ion, the species produced by
the loss of a proton from nitrous acid, is a potential acceptor of a proton from a suitable donor. It
is this reaction that causes an aqueous solution of sodium nitrite to be slightly basic:

NO2− + H2O ↔ HNO2 + OH- (3.7)

base1 acid2 conjugate conjugate
acid1 base2

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Amphiprotic species
Species that possess both acidic and basic properties are amphiprotic.

1. A dihydrogen phosphate ion, H2PO4- which behaves as a base in the presence of a proton
donor such as H3O+. In the presence of a proton acceptor, such as hydroxide ion however,
H2PO4 behaves as an acid and donates a proton to form the conjugate base HPO42-

H2PO− 4 + H3O+ ↔ HPO42- + H2O (3.8)

base1 acid2 acid1 base2

H2PO−4 + OH- -
↔ HPO2−
4 + H2O (3.9)
acid1 base2 base2 acid2

2. Water is the classic example of an amphiprotic solvent. Water can either as acts as an acid
or as a base depending on the solute. Other common amphiprotic solvents are methanol,
ethanol, and anhydrous acetic acid.

H2O + H2O ↔ H3O+ + OH- (3.10)

base1 acid2 acid1 base2

3. Other solvents such as methanol, ethanol and anhydrous acetic acid

NH3 + CH3OH ↔ NH4 + + CH3O- (3.11)

base1 acid2 acid1 base2

CH3OH + HNO2 ↔ CH3OH2 + + NO2 - (3.12)

base1 acid2 acid2 base2

Autoprotolysis
Amphiprotic solvents undergo self-ionization, or autoprotolysis, to form a pair of ionic species.
Autoprotolysis is yet another example of acid/base behaviour.

base1 + acid2 ↔ acid1 + base2

H2O + H2O ↔ H3O+ +OH-

CH3OH+ CH3OH ↔ CH3OH2+ + CH3O-
HCOOH + HCOOH↔ HCOOH2+ + HCOO-
NH3+NH3↔ NH4+ + NH2

The extent to which water undergoes autoprotolysis at room temperature is slight. Thus, the
hydronium and hydroxide ion concentrations in pure water are only about 10 -7 M. Despite the
small values of these concentrations, this dissociation reaction is of utmost importance in
understanding the behaviour of aqueous solutions.

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The tendency of a solvent to accept or donate protons determines the strength of a solute acid
or base dissolved in it. For example, perchloric and hydrochloric acids are strong acids in water.
If anhydrous acetic acid, a weaker proton acceptor than water, is substituted as the solvent,
neither of these acids undergoes complete dissociation; instead, equilibria such as the following
are established:

CH3COOH + HClO4↔ CH3COOH2+ + ClO−

4
base1 acid2 acid1 base2

Strongest acid HClO4 + H2O ↔ H3O++ ClO− 4 Weakest base

+ -
HCl + H2O ↔ H3O + Cl
H3PO4 + H2O ↔H3O++ H2PO− 4
Al(H2O)3+
6 + H2 O ↔ H3 O+
+ AlOH(H 2+
2O)5
+ −
HC2H3O2 + H2O ↔ H3O + C2H3O2
H2PO4 + H2O ↔ H3O+ + HPO2− 4
Weakest acid NH4 + H2O ↔ H3O++ NH3 Strongest base

Perchloric acid is, however, considerably stronger than hydrochloric acid in this solvent, its
dissociation being about 5000 times greater. Differentiating and levelling solvents also exist
for bases.

Differentiating solvent
Acetic acid thus acts as a differentiating solvent toward the two acids by revealing the inherent
differences in their acidities. In a differentiating solvent, various acids dissociate to different
degrees and have different strengths.

Levelling solvent
Water, on the other hand, is a levelling solvent for perchloric, hydrochloric, and nitric acids
because all three are completely ionized in this solvent and show no differences in strength. In
a levelling solvent, several acids are completely dissociated and show the same strength.

3.1.3 Chemical Equilibrium

Chemical equilibrium is a state wherein the ratio of concentrations of reactants and products is
constant.

Fig 3.3 Chemical Equilibrium in aqueous solution

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Equilibrium- constant expressions are algebraic equations that describe the concentration
relationships existing among reactants and products at equilibrium. Among other things,
equilibrium-constant expressions permit calculation of the error in an analysis resulting from the
quantity of unreacted analyte that remains when equilibrium has been reached.

Consider the chemical reaction

H3AsO4 + 3I- + 2H+ ↔ H3AsO3 + I3− + H2O (3.13)

Orange-red color

The rate of this reaction and the extent to which it proceeds to the right can be readily judged by
observing the orange-red color of the triiodide ion I3-.(The other participants in the reaction are
colorless.) If, for example, 1 mmol of arsenic acid, H3AsO4, is added to 100 mL of a solution
containing 3 mmol of potassium iodide, the red color of the triiodide ion appears almost
immediately. Within a few seconds, the intensity of the color becomes constant, which shows that
the triiodide concentration has become constant

A solution of identical color intensity (and hence identical triiodide concentration) can also be
produced by adding I mmol of arsenous acid, H3AsO3, to 100 mL of a solution containing 1 mmol
of triiodide ion. Here, the color intensity is initially greater than in the first solution but rapidly
decreases as a result of the reaction

H3AsO3 + I3− + H2O ↔ H3AsO3 + 3I- + 2H+ (3.14)

Ultimately, the color of the two solutions is identical. Many other combinations of the four
reactants can be used to yield solutions that are indistinguishable from the two just described.

The Le Chatelier principle states that the position of

equilibrium always shifts in such a direction as to relieve a stress
that is applied to the system.

In an analysis, the effect of introducing an additional amount of a participating species to the

reaction mixture is particularly important. Here, the resulting stress is relieved by a shift in
equilibrium in the direction that partially uses up the added substance. Thus, for the equilibrium
we have been considering the addition of arsenic acid (H3AsO4) or hydrogen ions causes an
increase in color as more triiodide ion and arsenous acid are formed; the addition of arsenous acid
has the reverse effect.

An equilibrium shift brought about by changing the amount of one of the participating
species is called a mass-action effect.

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3.1.4 Equilibrium constant equation

Equilibrium constant equation describe the influence of concentration (or pressure if the species
are gases) on the position of a chemical equilibrium. It predicts the direction and completeness of
a chemical reaction, however, yields no information concerning the rate at which equilibrium is
approached.

Consider a generalized equation for a chemical equilibrium

Ww + xX ↔Yy + zZ (3.15)

where the capital letters represent the participating chemical species and the lowercase italic letters
are the small whole numbers required to balance the equation.

Thus, the equation states that w moles of W react with x moles of X to form y moles of Y and z
moles of Z.

The equilibrium-constant expression for this reaction is

[𝒀]𝒚 [𝒁]𝒛
K = [𝑾]𝒘 [𝑿]𝒙 (3.16)

where the square-bracketed terms have the following meanings:

1. molar concentration if the species is a dissolved solute .

2. partial pressure in atmospheres if the species is a gas. The square bracketed was replaced
with the symbol pz which stands for the partial pressure of the gas Z in atmospheres.

If one (or more) of the species is a pure liquid, a pure solid, or the solvent present in excess, no
term for this species appears in the equilibrium constant expression.

Then equation 3.16 becomes equation 3.17.

[𝒀]𝒚
K= (3.17)
[𝑾]𝒘 [𝑿]𝒙

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Table 3.2 Equilibria and Equilibrium Constants

Name and
Symbol of Equilibrium-Constant
Type of Equilibrium Typical Example
Equilibrium Expression
Constant
Ion-product
Dissociation of water 2H2O ↔ H3O+ + OH- Kw= [H3O+][OH-]
constant, Kw

Heterogeneous equilibrium
Solubility BaSO4(S)↔ Ba2+ +
between a slightly soluble Kw = [Ba2+][SO2−
4 ]
product, Ksp SO2−
4
substance and its ions in a saturated solution

CH3COOH + H2O ↔ [𝑯𝟑 𝑶][𝑪𝑯𝟑 𝑪𝑶𝑶]

Dissociation H3O+ + CH3COO- Ka = [𝑪𝑯𝟑 𝑪𝑶𝑶𝑯]
Dissociation of a weak
constant.
acid or base [𝑶𝑯][𝑪𝑯𝟑 𝑪𝑶𝑶𝑯]
Kaor Kb CH3COO- + H2O ↔ Kb =
OH- + CH3COOCH [𝑪𝑯𝟑 𝑪𝑶𝑶]

Formation Ni2+ + 4CN ↔ [𝑵𝒊(𝐂𝐍)𝟐−

Formation of a complex ion Β4 = [𝑵𝒊𝟐+][𝑪𝑵𝟒−]𝟒
constant, βn Ni(CN)2−4

MnO4 + 5Fe2+ + 8H
Oxidation/reduction [𝑴𝒏𝟐+ ][𝑭𝒆𝟑+ ]𝟓
Kredox ↔ Mn2+ + 5Fe3+ + Kw = [𝑴𝒏𝐎− ][𝐅𝐞𝟐+ ]𝟓[𝐇+ ]𝟖
Equilibrium 𝟒
4H2O

Distribution equilibrium for a

solute between immiscible Kd I2(aq)↔ I2 (org) [𝑰𝟐 ]𝒐𝒓𝒈
Kw =
solvents [𝑰𝟐 ]𝒂𝒒

Table 3.3 Variation of Kw with temperature

Temperature, °C Kw
0 0.114 X 10-14
25 1.01 X 10-14
50 5.47 X 10-14
100 49 X 10-14

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Example 3.1

Calculate the hydronium and hydroxide ion concentrations of pure water at 25°C.

Step 1. Create the chemical expression

H20 ↔ H+ + OH-
Step 2. Determine the equilibrium concentration

Let x as the concentration of water that dissociate

H20 ↔ H+ + OH-
Initial H20 - -
Δ x x x
Equilibrium H2O-x x x
Step 3. Create an equilibrium expression
[Product]
K = [ ]
Reactant
X2
K = [H2 O−x]

K[H2 O − x] = x2

Kw = x2 but Kw at 25oC is 1.01 x 10-14

1.01 x 10-14 = x
x = [H ] = [OH-] = 7.00 x 10-7 M
+
at 25oC

Example 3.2

Calculate the hydronium and hydroxide ion concentrations and the pH and pOH of 0.200
M aqueous NaOH at 25°C.

Required : [H3O+], [OH-], pH, pOH

Sodium hydroxide is a strong electrolyte, and its contribution to the hydroxide ion
concentration in this solution is 0.200 mol/L.

NaOH  Na++ OH-

Initial (M) 0.20 0 0
Change (M) 0.20 0.20 0.20
---------------------------------------------------------------------------------------------------
Final (M) 0 0.20 0.20

[OH-] = 0.20M
pOH = -log [OH-]
pOH = -log (0.20)
pOH = 0.699

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𝐾𝑤 1.00 𝑥 10−14
[H3O+] = = = 5.00 x 10-14
𝑂𝐻− 0.200

pH = -log 0.5000 x 10-14 = 13.301

or it could be like this

pH + pOH = 14
pH = 14 - pOH
pH = 14 - 0.699
pH = 13.301
[H3O+] = e-log pH
[H3O+] = e-log 13.301
[H3O+] = 5.00 x 10-14 M

3.1.5 Solubility Product Constant

Most, but not all, sparingly soluble salts are essentially completely dissociated in saturated aqueous
solution. For example, when an excess of barium iodate is equilibrated with water, the dissociation
process is adequately described by the equation

Ba(IO3)2(s)↔ Ba2+ (aq) + 2IO −

3 (aq)

[𝑩𝒂𝟐+ ][𝐈𝐎− 𝟑]
𝟐
K= [𝑩𝒂(𝑰𝑶
𝟑 )𝟐 (𝒔)]

K[𝑩𝒂(𝑰𝑶𝟑 )𝟐 (𝒔)]= Ksp = [𝑩𝒂𝟐+][𝐈𝐎 −

𝟑]
𝟐
(3.18)

where the new constant is called the solubility-product constant or the solubility product. It is
important to appreciate that Equation 4-18 shows that 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 milligrams or several grams.

A table of solubility-product constants for numerous inorganic salts is found in Appendix 2. The
examples that follow demonstrate some typical uses of solubility product expressions. Further
applications are considered in later chapters.

Example 3.3

How many grams of of Ba(IO3)2 (487 g/mol) can be dissolved in 500 mL of water at 25°C?

Required : Mass

Reaction : Ba(IO3)2  Ba+2 + 2(IO3)

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Ba(IO3)2  Ba+2 + 2(IO3)

Initial (M) X 0 0
Change (M) X X 2X
---------------------------------------------------------------------------------------------------
Final (M) - X 2X

𝑋 (2𝑋)2
𝐾 = [𝐵𝑎(𝐼𝑂3)2]

𝐾 [𝐵𝑎(𝐼𝑂3 )2 ] = 4𝑋 3

𝐾𝑠𝑝𝐵𝑎(𝐼𝑂3 )2 = 4𝑋 3

Based on Appendix 2 of Fundamental of Analytical chemistry

𝐾𝑠𝑝𝐵𝑎(𝐼𝑂3 )2 = 1.57 𝑥 10−9
𝑀𝑊𝐵𝑎(𝐼𝑂3 )2 =

1.57 𝑥 10−9 = 4𝑋 3
3 1.57𝑥10−9
𝑋 = [[𝐵𝑎(𝐼𝑂3 )2 ]] = √
4

X = 7.30x10-4 M

The effect of a common ion on the solubility of a precipitate

The common-ion effect is a mass-action effect predicted from the Le Chatelier principle and is
demonstrated by the following examples.

Example 3.4

Calculate the molar solubility of Ba (IO3)2 in a solution that is 0.0200 M in Ba (NO3)2.

Reaction : Ba(IO3)2  Ba+2 + 2(IO3)

Initial (M) X 0.0200 0
Change (M) X X 2X
----------------------------------------------------------------------------------------
Final (M) - 0.020+X 2X

K Ba(IO3)2 = (0.020-X)(2X)2

1.57X10-9 = (0.020+X)(2X)2

X = 1.3960 x10-4 M

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Example 3.5

Calculate the solubility of Ba(IO3)2 in a solution prepared by mixing 200 mL of 0.0100 M

Ba(NO3)2 with 100 mL of 0.100 M NaIO3.

Moles of each reactant

Ba(NO3)2 = 200mL (0.01mmol/mL) = 2 mmol
NaIO3 = 100mL (0.1mmol/mL) = 10mmol

Reaction involved in solvent :

Ba(NO3)2 + 2 NaIO3  Ba(IO3)2 + 2NaNO3

In very 1 mole of Ba(NO3)2 , it requires 2 moles of 2 NaIO3

Thus:
Limiting reactant - Ba(NO3)2
Excess reactant - NaIO3
2𝑚𝑚𝑜𝑙 𝑁𝑎𝑁𝑂3
Amount of NaIO3 in excess = 10mmol NaIO3 – 2 mmol Ba(NO3)2 1 𝑚𝑚𝑜𝑙 𝐵𝑎(𝑁𝑂3)2

Amount of NaIO3 in excess = 6 mmol NaIO3

6 𝑚𝑚𝑜𝑙 𝑁𝑎𝐼𝑂3
[NaIO3] = (200𝑚𝑙+100 𝑚𝑙)𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

[NaIO3] = 0.02M

For Ba(IO3)2

Reaction : Ba(IO3)2  Ba+2 + 2(IO3)

Initial (M) X 0 0.02
Change (M) X X 2X
---------------------------------------------------------------------------------------------------
Final (M) - X 0.02+ 2X

K Ba(IO3)2 = (X)(0.02+2X)2

1.57X10-9 = (X)(0.02+2X)2

X = 3.9219 x10-6 M

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3.1.6 Acid-Base Dissociation Constant

When a weak acid or a weak base is dissolved in water, partial dissociation occurs. Thus, for
nitrous acid, we can write

[𝑯𝟑 𝑶+ ][𝐍𝐎−
𝟐]
HNO2 + H2O ↔ H3O+ + NO−
2 Ka = [𝑯𝑵𝑶𝟐]

where Ka is the acid dissociation constant for nitrous acid. In an analogous way, the base
dissociation constant for ammonia is

[𝐍𝑯+ −
𝟒 ][𝑶𝑯 ]
NH3 + H2O ↔ N𝐻4++ OH- Kb = [𝑵𝑯𝟑 ]

Note that [H2O] does not appear in the denominator of either equation because the concentration
of water is so large relative to the concentration of the weak acid or base that the dissociation does
not alter [H2O] appreciably. Just as in the derivation of the ion-product constant for water, [H2O]
is incorporated into the equilibrium constants Ka and Kb. Dissociation constants for weak acids are
found in Appendix 3 of Fundamentals of Analytical Chemistry by Skoog et al.

Dissociation constants for conjugate acid/base pairs

Consider the base dissociation-constant expression for ammonia and the acid dissociation constant
expression for its conjugate acid, ammonium ion:

[𝐍𝐇𝟒+ ][𝑶𝑯− ]
NH3 + H2O ↔ NH4+ + OH- Kb = [𝑵𝑯𝟑 ]

[𝑵𝑯𝟑 ][𝑯𝟑 𝑶+ ]
NH4+ + H2O ↔ NH3 + H3O+ Ka = [𝐍𝐇𝟒+ ]

Multiplication of one equilibrium-constant expression by the other gives

[𝑁H3][OH− ] [NH+ −
4 ][OH ]
KbKa = x = [H3 O+] [OH−]
[NH+
4] [NH3 ]

but
Kw = [H3 O+] [OH− ]

and therefore
Kw = KaKb (3.19)

[H3 O+ ][NH3 ]
NH4+ + H2O ↔ H3O+ + NH3 Ka = = 5.70 x 10-10
[NH+
4]

and we can write NH3 + H2O ↔ NH4+ + OH-

[𝐍𝐇𝟒+ ][𝐎𝐇 − ] 𝐊𝐰 𝟏.𝟎𝟎𝐱𝟏𝟎−𝟏𝟒

Kb = = = 𝟓.𝟕𝟎𝐱𝟏𝟎−𝟏𝟎 = 1.75 x 10-5
[𝐍𝐇𝟑] 𝐊𝐚

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Example 3.6

What is Kb for the equilibrium?

CN- + H2O ↔ HCN + OH-

Appendix 3 lists a Ka value of 6.2 X 10-10 for HCN. Thus,

Kw [HCN][OH−]
Kb = =
Ka [CN− ]

𝟏𝐱𝟏𝟎−𝟏𝟒
Kb = 𝟔.𝟐𝐱𝟏𝟎−𝟏𝟎 = 1.61 x 10-

Hydronium ion concentration of solutions of weak acids

When the weak acid HA is dissolved in water, two equilibria are established that yield hydronium
ions:
[H3 O+ ][A− ]
HA + H2O ↔ H3O+ + A- Ka =
[HA]

2H2O ↔ H3O+ + OH- Kw = [H3O+][OH-]

[A-] = [H3O+]

Example 3.7

Calculate the hydronium ion concentration in 0.120 M nitrous acid. The principal
equilibrium is

𝐻𝑁𝑂2 + 𝐻2 𝑂 ↔ 𝐻3 𝑂+ + 𝑁𝑂2−

for which (see Appendix 2)

[𝐻3 𝑂+][𝑁𝑂2− ]
𝐾𝑎 = 7.1𝑥10−4 =
[𝐻𝑁𝑂2 ]
[𝐻𝑁𝑂2 ] = 0.120 − [𝐻3 𝑂+ ]

When these relationships are introduced to the expression for Ka, we obtain

[𝐻3 𝑂 +]2
𝐾𝑎 = = 7.1𝑥10−4
0.120 − [𝐻3 𝑂+ ]

[𝑯𝟑 𝑶+] = 𝟖. 𝟖𝟖𝟐𝟐 𝒙𝟏𝟎−𝟑𝑴

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CHE 401 : ANALYTICAL CHEMISTRY

We now examine the assumption that 0.120 - 0.0092 = 0.120 and see that the error is about 8%. If
a more accurate figure is needed, solution of the quadratic equation yields 8.9 X 10 -3 M for the
hydronium ion concentration.

Example 3.8

Calculate the hydronium ion concentration in a solution that is 2.0 X 10 -4 M in aniline

hydrochloride, C6H5NH3Cl.

C6H5NH3Cl  C6H5NH3+ + Cl-

C6H5NH3+ + H2O ↔ C6H5NH2+ + H3O+

Initial 2.0 X 10-4 - -

Change x x x
---------------------------------------------------------------------------------
Equilibrium 2.0 X 10-4 – x x x

𝑋2
𝐾𝑎 = Ka of C6H5NH3+ = 2.51 x 10-5
2.0 𝑥 10−4 −𝑋

𝑋2
2.51 x 10-5 = 2.0 𝑥 10−4 −𝑋

X = [H3O+] = 5.9405 x 10-5 M

Hydronium ion concentration of solutions of weak bases

The techniques discussed in previous sections are readily adapted to the calculation of the
hydroxide or hydronium ion concentration in solutions of weak bases.

Aqueous ammonia is basic by virtue of the reaction

𝑵𝑯𝟑 + 𝑯𝟐 𝑶 ⇌ 𝑵𝑯𝟒 + + 𝑶𝑯−

The predominant species in such solutions has been clearly demonstrated to be

NH3. Nevertheless, solutions of ammonia are still called ammonium hydroxide occasionally
because at one time chemists thought that NH3OH rather than NH3 was the undissociated form of
the base. Application of the mass law to the equilibrium as written yields

[𝑵𝑯𝟒 +][𝑶𝑯− ]
𝑲𝒃 =
𝑵𝑯𝟑

Example 3. 9

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CHE 401 : ANALYTICAL CHEMISTRY

Calculate the hydroxide ion concentration of a 0.0750 M NH3 solution. The predominant
equilibrium is
𝑁𝐻3 + 𝐻2 𝑂 ⇌ 𝑁𝐻4 + + 𝑂𝐻 −

𝑁𝐻3 + 𝐻2 𝑂 ⇌ 𝑁𝐻4 + + 𝑂𝐻 −

Initial 0.075 - -
Change x x x
------------------------------------------------------------------
Equi 0.075-x x x

𝑋2
Kb = but Ka (NH4+) = 5.70 x10-10
0.075−𝑋

𝐾𝑤 1.0 𝑥 10−14 𝑋2
Kb = = =
𝐾𝑎 5.70 𝑥 10−10 0.075−𝑋

𝒙 = [𝑶𝑯− ] = 𝟏. 𝟏𝟑𝟖𝟑 𝒙𝟏𝟎−𝟑 𝑴

Example 3. 10

Calculate the hydroxide ion concentration in a 0.0100 M sodium hypochlorite solution.

NaOCl  Na+ + OCl-

OCl- + H2O ⇌ HOCl + OH-

Initial 0.010 - -
Change x x x
-----------------------------------------------------------------------------
Equilibrium 0.010 – x x x

[𝐻𝑂𝐶𝑙][𝑂𝐻 − ] 𝐾𝑤
𝐾𝑏 = [𝑂𝐶𝑙− ]
= 𝐾𝑎 (𝐻𝑂𝐶𝑙) = 3 𝑥 10−8
𝐾𝑎

1.01 𝑥 10−14 𝑥2
𝐾𝑏 = =
3 𝑥 10−8 0.01−𝑥

𝒙 = [𝑶𝑯− ] = 𝟓. 𝟕𝟖𝟓𝟓 𝒙 𝟏𝟎−𝟓 𝑴

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CHE 401 : ANALYTICAL CHEMISTRY

3.2 BUFFER SOLUTION

By definition, a buffer solution resists changes in pH with dilution or with addition of acids or
bases. Generally, buffer solutions are prepared from a conjugate acid/base pair, such as acetic
acid/sodium acetate or ammonium chloride/ammonia.

Calculation of the pH of Buffer Solutions

A solution containing a weak acid, HA, and its conjugate base, A-, may be acidic, neutral, or basic,
depending on the position of two competitive equilibria:

[𝐻3 𝑂+ ][𝐴− ]
HA + 𝐻2 𝑂 ⇌ 𝐻3 𝑂+ + 𝐴− 𝐾𝑎 = [HA]

[𝑂𝐻 − ][𝐻𝐴]
𝐴− + 𝐻2 𝑂 ⇌ 𝑂𝐻 − + 𝐻𝐴 𝐾𝑏 = [𝐴− ]

3.2.1 The Henderson-Hasselbalch Equation

The Henderson-Hasselbalch equation, which is used to calculate the pH of buffer solutions, is

frequently encountered in the biological literature and biochemical texts.

𝐶
-log[𝐻3 𝑂+] = −log𝐾𝑎 + 𝑙𝑜𝑔 𝐶𝑁𝐴
𝐻𝐴

Therefore,
𝐶
pH = pKa + 𝑙𝑜𝑔 𝐶𝑁𝐴 (3.20)
𝐻𝐴

We can also use this formula in computing for the pOH-

𝐶
-log[OH−] = −log𝐾𝑏 + 𝑙𝑜𝑔 𝐶𝐻𝐴−
𝐴

Therefore,
𝐶
pOH = pKb + 𝑙𝑜𝑔 𝐶𝐻𝐴− (3.21)
𝐴

Example 3.11

What is the pH of a solution that is 0.400 M in formic acid and 1.00 M in sodium formate?

The pH of this solution will be affected by the Kw of formic acid and the Kb of formate ion.

HCOOH + H2O ⇌ 𝐻3 𝑂+ + 𝐻𝐶𝑂𝑂− Ka= 1.80 X 10-4

Kw
𝐻𝐶𝑂𝑂− + 𝐻2 𝑂 ⇌ 𝐻𝐶𝑂𝑂𝐻 + 𝑂𝐻 − Kb= = 5.56 X 10-11
𝐾𝑎
Since the Ka for formic acid is orders of magnitude larger than the Kb for formate, the
solution will be acidic and Kawill determine the H3O+ concentration. We can thus write

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CHE 401 : ANALYTICAL CHEMISTRY

[𝐻3 𝑂+][𝐻𝐶𝑂𝑂 −]
𝐾𝑎 = = 1.80𝑥10−4
𝐻𝐶𝑂𝑂𝐻

[HCOO-] = CHCOO-= 1.00 M

[HCOOH] = CHCOOH= 0.400 M

𝟎. 𝟒𝟎𝟎
[𝑯𝟑 𝑶+ ] = 𝟏. 𝟖𝟎𝒙𝟏𝟎−𝟒 𝒙 = 𝟕. 𝟐𝟎𝒙𝟏𝟎−𝟓 𝑴
𝟏. 𝟎𝟎

Note that the assumption that [H3O+] « CHCOOH and that [H3O+] « CHCOO is valid.

Thus,
pH = -log (7.20 X 10-5) = 4.14

Example 3.12

Calculate the pH of a solution that is 0.200 M in NH3 and 0.300 M in NH4Cl.

ln Appendix 3, we find that the acid dissociation constant Ka for NH4+ is 5.70 x 10-10.

Using Henderson-Hasselbalch equation:

𝐶
-log[OH−] = −log𝐾𝑏 + 𝑙𝑜𝑔 𝐶𝐻𝐴−
𝐴

1.01 𝑥 10−14 0.30

𝑝𝑂𝐻 = − log 5.70 𝑥 10−10 + log 0.20

𝑝𝑂𝐻 = 4.9276

𝒑𝑯 = 14 – 4.9271 = 9.0723

3.2.2 Properties of Buffer Solutions

In this section, we illustrate the resistance of buffers to changes of pH brought about by dilution
or addition of strong acids or bases.

The Effect of Dilution

Behavior of buffered and unbuffered solutions with dilution, for each the initial solute
concentration is 1.00 M. The resistance of the buffered solution changes in pH during dilution is
clear:

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CHE 401 : ANALYTICAL CHEMISTRY

Figure 3.3. The effect of dilution of the pH of buffered and unbuffered solutions. The
dissociation constant for HA is 1.00 X 10-4. Initial solute concentrations are 1.00 M

The effect of acids and bases

Example 3.13 illustrates a second property of buffer solutions, their resistance to pH change after
addition of small amounts of strong acids or bases.

Example 3.13

Calculate the pH change that takes place when a 100-mL portion of (a) 0.0500 M NaOH
and (b) 0.0500 M HCl is added to 400 mL of the buffer solution that was described in
Example 4-12.

(a) Addition of NaOH converts part of the NH4+ in the buffer to NH3.

𝑁𝐻4 + + 𝑂𝐻 − ⇌ 𝑁𝐻3 + 𝐻2 𝑂

The analytical concentrations of NH3 and NH4Cl then become

400𝑥0.200 + 100𝑥0.0500 85.0

𝐶𝑁𝐻3 = = = 0.170𝑀
500 500

400𝑥0.300 − 100𝑥0.0500 115

𝐶𝑁𝐻4 𝐶𝑙 = = = 0.230𝑀
500 500

When substituted into the acid dissociation-constant expression for NH4+, these values
yield

0.230
[𝐻3 𝑂+] = 5.70x10−10 𝑥 = 7.71𝑥10−10 𝑀
0.170

pH = -log 7.71 x 10-10 = 9.11

and the change in pH is
ΔpH = 9.11 - 9.07 = 0.04

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CHE 401 : ANALYTICAL CHEMISTRY

(b) Addition of HCl converts part of the NH3 to NH4-, thus,

NH3 + H3O+⇌ NH4+ + H2O

400𝑥0.200 − 100𝑥0.0500 75.0

𝐶𝑁𝐻3 = = = 0.150𝑀
500 500
400𝑥0.300 + 100𝑥0.0500 125
𝐶𝑁𝐻4 + = = = 0.250𝑀
500 500
0.250
[𝐻3 𝑂+] = 5.70x 10−10 𝑥 = 9.50𝑥10−10 𝑀
0.150
pH = -log 9.50 x 10-10 = 9.02

3.3.3 Weak Acid – Base ionization

%Δ
% Ionization = ---------------- (3.22)
Ci

%Δ
% Ionization = ------------------------------- (3.33)
Initial amount of reactant

Example 3.14

A solution of formic acid (HCOOH) is prepared by dissolving 1.15 grams of pure acid
and diluting to 250 mL
a) What is the concentration of the acid in mol/L
b) If the acid in this solution is 4.6% ionized, what is the molar concentration of H+.
1 𝑚𝑜𝑙𝑒 𝐻𝐶𝑂𝑂𝐻
(1.15 𝑔 𝐻𝐶𝑂𝑂𝐻)( )
1.01(2)+12.01(1)+16(2)𝑔
[𝐻𝐶𝑂𝑂𝐻] = 1𝐿
250𝑚𝐿 ( )
1000 𝑚𝐿

[𝐻𝐶𝑂𝑂𝐻] = 0.0999M

HCOOH ⇌ HCOO- + H+
Initial 0.0999 - -
Change x x x
------------------------------------------------------------------------------------
Equilibrium 0.0999-x x x

𝑥2
𝐾𝑎 = = 1.8 𝑥 10−4
0.0999−𝑥

𝒙 = [𝑯+ ] = 𝟒. 𝟏𝟓𝟏𝟓 𝒙 𝟏𝟎−𝟑 𝑴

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CHE 401 : ANALYTICAL CHEMISTRY

3.3 EFFECT OF ELECTROLYTES IN CHEMICAL EQUILIBRIA

Scientists throughout the world implemented a standardized system of units known as the
International System of Units (SI). This system is based on the seven basic units depicted in Table
2.1. From these base units are derived various other useful units, such as volts, hertz,

Experimentally, we find that the position of most solution equilibria depends on the electrolyte
concentration of the medium, even when the added electrolyte contains no ion in common with
those involved in the equilibrium. For example, consider again the oxidation of iodide ion by
arsenic acid that we described in Section 9B-1,

H3As04 + 3I- + 2H+⇌ H3AsO3 + I3-+ H2O

If an electrolyte, such as barium nitrate, potassium sulfate, or sodium perchlorate, is added to this
solution, the color of the triiodide ion becomes less intense. This decrease in color intensity
indicates that the concentration of I3- has decreased and that the equilibrium has been shifted to the
left by the added electrolyte.

Figure 3.4 Effect of electrolyte concentration on concentration-based equilibrium

3.3.1 The Effect of Ionic Strength

Systematic studies have shown that the effect of added electrolyte on equilibria is independent of
the chemical nature of the electrolyte but depends on a property of the solution called the ionic
strength. This quantity is defined as

𝟏
𝐢𝐨𝐧𝐢𝐜𝐬𝐭𝐫𝐞𝐧𝐠𝐭𝐡 = 𝛍 = ([𝑨]𝒁𝟐𝑨 + [𝑩]𝒁𝟐𝑩 + [𝑪]𝒁𝟐𝑪 + ⋯ ) (3.34)
𝟐

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CHE 401 : ANALYTICAL CHEMISTRY

where [A], [B], [C], … represents the species molar concentrations of ions A, B,C, … Z a, Zb, Zc,
… are their charges.

Figure 3.5 Effect of electrolyte concentration on the solubility of some salts.

Example 3.15

Calculate the ionic strength of

(a) a 0.1 M solution of KNO3 and
(b) a 0.1 M solution of Na2SO4.

(a) For the KNO3 solution, [K+] and [NO3-] are 0.1 M and

𝟏
𝛍= (𝟎. 𝟏𝑴𝒙𝟏𝟐 + 𝟎. 𝟏𝑴𝒙𝟏𝟐 ) = 𝟎. 𝟏𝑴
𝟐

(b) For the Na2S04 solution, [Na+] = 0.2 M and [SO24-] = 0.1 Therefore,

𝟏
𝛍= (𝟎. 𝟐𝑴𝒙𝟏𝟐 + 𝟎. 𝟏𝑴𝒙𝟐𝟐) = 𝟎. 𝟑𝐌
𝟐

Example 3.16

What is the ionic strength of a solution that is 0.05 M in KNO3 and 0.1 M in Na2S04?

𝟏
𝛍= (𝟎. 𝟎𝟓𝑴𝒙𝟏𝟐 + 𝟎. 𝟎𝟓𝑴𝒙1𝟐 + 𝟎. 𝟐𝑴𝒙𝟏𝟐 + 𝟎. 𝟏𝑴𝒙𝟐𝟐 ) = 𝟎. 𝟑𝟓𝐌
𝟐

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CHE 401 : ANALYTICAL CHEMISTRY

Table 3.4 Effect of Charge on Ionic Strength

Type Electrolyte Example Ionic Strength*

1:1 NaCl c
1:2 Ba(NO3)2, NA2SO4 3c
1:3 Al(NO3)3, Na3PO4 6c
2:2 MgSO4 4c
*c = molarity of the salt

3.3.2 Activity Coefficients

Chemists use a term called activity, a, to account for the effects of electrolytes on chemical
equilibria. The activity, or effective concentration, of species X depends on the ionic strength of
the medium and is defined by

ax= [X] λx (3.35)

where λxis the activity of the species X, [X] is its molar concentration, and λx is a dimensionless
quantity called the activity coefficient. The activity coefficient and thus the activity of X vary
with ionic strength such that substitution of axfor [X] in any equilibrium-constant expression
makes the equilibrium constant independent of the ionic strength. To illustrate, if Xm Ynis a
precipitate, the thermodynamic solubility product expression is defined by the equation

Ksp = axm x ayn (3.36)

Ksp=[X]m[Y]n · λxmλyn = K’sp · λxmλyn (3.37)

Here K’sp is the concentration solubility product constant and Ksp is the thermodynamic
equilibrium constant. The activity coefficients λx and λy vary with ionic strength in such a way
as to keep Ksp numerically constant and independent of ionic strength (in contrast to the
concentration constant, K’sp).

Properties of Activity Coefficients

Activity coefficients have the following properties:

1. The activity coefficient of a species is a measure of the effectiveness with which that
species influences an equilibrium in which it is a participant. In very dilute solutions, in
which the ionic strength is minimal, this effectiveness becomes constant, and the activity
coefficient is unity. Under such circumstances, the activity and the molar concentration are
identical (as are thermodynamic and concentration equilibrium constants), as the ionic

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CHE 401 : ANALYTICAL CHEMISTRY

strength increases, however, an ion loses some of its effectiveness, and its activity
coefficient decreases.

2. In solutions that are not too concentrated, the activity coefficient for a given species is
independent of the nature of the electrolyte and dependent only on the ionic strength.

3. For a given ionic strength, the activity coefficient of an ion departs farther whom unity as
the charge carried by the species increases. This effect is shown in Figure 4-4.

4. The activity coefficient of an uncharged molecule is approximately unity, regardless of

ionic strength.

5. At any given ionic strength, the activity coefficients of ions of the same charge are
approximately equal. The small variations that do exist can be correlated with the effective
diameter of the hydrated ions.

Figure 4b-3. Effect of ionic strength on activity coefficients.

6. The activity coefficient of a given ion describes its effective behavior in all equilibria in
which it participates. For example, at a given ionic strength, a single activity coefficient
for cyanide ion describes the influence of that species on any of the following equilibria:

HCN + H2O ⇌H3O+ + CN-

Ag++ CN ⇌ AgCN(s)
Ni2+ + 4CN⇌ Ni(CN)24-

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CHE 401 : ANALYTICAL CHEMISTRY

3.3.2 The Debye-Huckel Equation

In 1923,P. Debye and E. Huckel derive a theoretical expression that permits the calculation of
activity coefficients of ion from their charge and their average size. This equation takes the form

𝟎.𝟓𝟏𝟐𝟐𝒙√𝝁
− 𝐥𝐨𝐠 𝛌𝒙 = (3.38)
𝟏+𝟑.𝟑𝒂𝒙√𝝁
where
𝛌x= activity coefficient of the species X
Zx = charge on the species X
μ = ionic strength of the solution
ax= effective diameter of the hydrated ion X in nanometers (10-9m)

The constants 0.51 and 3.3 are applicable to aqueous solutions at 25°C; other values must be used
at other temperatures.

TABLE 3.5. ACTIVITY COEFFICIENTS FOR IONS AT 25℃

Activity Coefficient at Indicated Ionic Strength
Ion 𝜶𝑿 , nm 0.001 0.005 0.01 0.05 0.1
+
H3O 0.9 0.967 0.934 0.913 0.85 0.83

Li+, C6H5COO- 0.6 0.966 0.930 0.907 0.83 0.80

Na+, 𝐈𝐎− − − −
𝟑 , 𝐇𝐒𝐎𝟑 ,𝐇𝐂𝐎𝟑 , 𝐇𝟐 𝐏𝐎𝟒 , 𝐇𝟐 𝐀𝐬𝐎𝟒 ,
−
- 0.4-0.45 0.965 0.927 0.902 0.82 0.77
OAc
OH-, F-, SCN-, HS-, 𝐂𝐥𝐎𝟑− , 𝐂𝐥𝐎− − −
𝟒 , 𝐁𝐫𝐎𝟑 , 𝐈𝐎𝟑 ,
− 0.35 0.965 0.926 0.900 0.81 0.76
𝐌𝐧𝐎𝟒
K+, Cl-, Br-, I-, CN-, 𝐍𝐎− −
𝟐 , 𝐍𝐎𝟑 , HCO𝐎
−
0.3 0.965 0.925 0.899 0.81 0.75

Rb+, Cs+, Tl+, Ag+, 𝐍𝐇𝟒+ 0.25 0.965 0.925 0.897 0.80 0.75

Mg2+, Be2+ 0.8 0.872 0.756 0.690 0.52 0.44

Ca2+, Cu2+, Zn2+, Sn2+, Mn2+, Fe2+, Ni2+, Co2+,
0.6 0.870 0.748 0.676 0.48 0.40
Phthalate2-
Sr2+, Ba2+, Cd2+, Hg2+, S2- 0.5 0.869 0.743 0.668 0.46 0.38

Pb2+, 𝐂𝐎𝟐− 𝟐− 𝟐−
𝟑 , 𝐒𝐎𝟑 , 𝐂𝟐 𝐎𝟒 0.45 0.868 0.741 0.665 0.45 0.36

𝐇𝐠 𝟐+ 𝟐− 𝟐− 𝟐− 𝟐−
𝟐 , 𝐒𝐎𝟒 , 𝐒𝟐 𝐎𝟑 , 𝐂𝐫𝟒 , 𝐇𝐏𝐎𝟒 0.40 0.867 0.738 0.661 0.44 0.35

Al3+, Fe3+, Cr3+, La3+, Ce3+ 0.9 0.737 0.540 0.443 0.24 0.18

𝐏𝐎𝟑− 𝟑−
𝟒 , 𝐅𝐞(𝐂𝐍)𝟔 0.4 0.726 0.505 0.394 0.16 0.095

Th4+, Zr4+, Ce4+, Sn4+ 1.1 0.587 0.348 0.252 0.10 0.063

𝐅𝐞(𝐂𝐍)𝟒−
𝟔 0.5 0.569 0.305 0.200 0.047 0.020
Source: Reprinted with permission from J. Kielland, J. Am. Chem. Soc., 1937, 59, 1675,
Copyright 1937 American Chemical Society.

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CHE 401 : ANALYTICAL CHEMISTRY

Example 3.17

(a) Use Equation 4-33 to calculate the activity coefficient for Hg2+ in a solution that has
an ionic strength of 0.085 M. Use 0.5 nm for the effective diameter of the ion.
(b)
(b) Compare the value obtained in (a) with the activity coefficient obtained by linear
interpolation of the data in Table 4-5 for coefficients of the ion at ionic strengths of 0.1 M
and 0.05 M.

(0.51)(2)√0.085
(a) − log λ𝐻𝑔2+ = 1+(3.3)(0.5)√0.085 = 0.4016

λ𝐻𝑔2+ = 10−0.4016 = 0.397 = 0.40

(b) From Table 3.5

𝝁𝛌𝑯𝒈𝟐+
0.1M 0.38
0.05M 0.46

When Δμ = (0.10 M - 0.05 M) = 0.05 M, Δλ𝐻𝑔2+ = 0.46 - 0.38 = 0.08 at an ionic strength
of 0.085 M.

Δμ = (0.100 M - 0.085 M) = 0.015 M

and
0.015
Δλ𝐻𝑔2+ = 𝑥 0.08 = 0.024
0.05

Thus,
𝛌𝑯𝒈𝟐+ =0.38 + 0.024 = 0.404 = 0.40

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CHE 401 : ANALYTICAL CHEMISTRY

3.4 END OF MODULE TEST

Aqueous Solutions

1. Briefly describe or define and give an example of

a. a weak electrolyte.
b. Bronsted-Lowry acid.
c. the conjugate acid of a Bronsted-Lowry base.
d. an amphiprotic solvent.
e. a zwitterion
f. autoprotolysis.
g. a strong acid.
h. the Le Chatelier principle
i. the common-ion effect.
2. Briefly describe or define and give an example of
a. an amphiprotic solute.
b. a differentiating solvent.
c. a leveling solvent.
d. a mass-action effect.

3. Briefly explain why there is no term in an equilibrium constant expression for water or
for a pure solid, even though one (or both) appears in the balanced net ionic equation
for the equilibrium.

4. Identify the acid on the left and its conjugate base on the right in the following
equations:
a. HOCl + H2O ⇄ H3O+ + OCl-
b. HONH2 + H2O ⇄ HONH2 + OH-
c. NH4+ + H2O ⇄ NH3 + H3O+
d. 2HCO−3 ⇄ H2C03 + CO2− 3
e. PO3− 4 + H2PO −
4 ⇄ 2HPO 2−
4
5. Write expressions for the autoprotolysis of
a. H2O.
b. CH3COOH.
c. CH3NH2.
d. CH3OH.
6. Write the equilibrium-constant expressions and obtain numerical values for each constant in
a. the basic dissociation of ethyl amine, C2H5NH2•
b. the acidic dissociation of hydrogen cyanide, HCN.
c. the acidic dissociation of pyridine hydrochloride, C 5H5NHCl.
d. the basic dissociation of NaCN.
e. the dissociation of H3AsO4 to H3O+ and AsO3− 4 .
f. the reaction of CO2−3 with H 2 O to give H 2 C0 -
3and OH .
7. Generate the solubility-product expression for
a. CuI.
b. PbI2.
c. BiI3

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CHE 401 : ANALYTICAL CHEMISTRY

d. MgNH4PO4
8. Calculate the solubility-product constant for each of the following substances, given that the
molar concentrations of their saturated solutions are as indicated:
a. CuSeO3 (1.42 X 10-4 M).
b. Pb(IO3)2 (4.3 X 10-5M).
c. SrF2 (8.6 X 10-4 M).
d. Th(OH)4 (3.3 X 10-4 M).

9. What CrO2−
4 concentration is required to
a. initiate precipitation of Ag2CrO4 from a solution that is 3.41 X 10-2 M in Ag+?
b. lower the concentration of Ag+ in a solution to 2.00 x 10-6 M?

10. What hydroxide concentration is required to

a. initiate precipitation of Al3+ from a 2.50 X 10-2 M solution of Al2(S04)3?
b. lower the AI3+ concentration in the foregoing solution to 2.00 X 10 -7 M?

11. The solubility-product constant for Ce(IO3)3 is 3.2 X 10-10. What is the Ce3+ concentration in a
solution prepared by mixing 50.0 mL of 0.0250 M Ce3+ with 50.00 mL of water?
a. 0.040 M IO−3 ?
b. 0.250 M IO−3 ?
c. 0.150 M IO−3 ?

12. The solubility-product constant for K2PdCl6 is 6.0 x 10 -6 (K2PdCI6 ⇄ 2K+ + PdCI62− ). What
is the K+ concentration of a solution prepared by mixing 50.0 mL of 0.200 M KCl with 50.0
mL of
a. 0.0500 M PdCI62− ?
b. 0.100 M PdCI62− ?
c. 0.200 M PdCI62− ?

13. The solubility products for a series of iodides are

a. CuI Ksp = I X 10-12
b. AgI Ksp = 8.3 X 10-17
c. Pbl2 Ksp = 7.1 X 10-9
d. BiI3 Ksp = 8.1 X 10-19

List these four compounds in order of decreasing molar solubility in

a. water.
b. 0.10 M NaI.
c. 0.010 M solution of the solute cation.

14. The solubility products for a series of hydroxides are

BiOOH Ksp = 4.0 X 10-10 = [BiO+] [OH-]

Be(OH)2 Ksp = 7.0 X 10-22
Tm(OH)3 Ksp = 3.0 X 10-24
Hf(OH)4 Ksp = 4.0 X 10-26

Which hydroxide has

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CHE 401 : ANALYTICAL CHEMISTRY

(a) the lowest molar solubility in H2O?

(b) the lowest molar solubility in a solution that is 0.10 M in NaOH?

15. At 25°C, what are the molar H3O+ and OH- concentrations in
a. 0.0300 M HOCl?
b. 0.0600 M butanoic acid?
c. 0.100 M ethylamine?
d. 0.200 M trimethylamine?
e. 0.200 M NaOCI?
f. 0.0860 M CH3CH2COONa?
g. 0.250 M hydroxylamine hydrochloride?
h. 0.0250 M ethanolamine hydrochloride?

16. What is a buffer solution, and what are its properties?

17. What weight of sodium formate must be added to 400.0 mL of 1.00 M formic acid to
produce a buffer solution that has a pH of 3.50?

18. From the fact that acetic acid (CH3COOH) is 1.30% ionized in 0.10M of aqueous
solution, calculate
a. Ionization constant of acetic acid
b. Percentage ionization in 0.20M solution

19. What would be the H+ ion concentration in a solution 0.10M in acetic acid
containing sufficient dissolved acetate ion concentration of 1.5M.

31