CHM 222 (3 Units)

ANALYTICAL CHEMISTRY
Lecture Note

CHM 222_ Analytical Chemistry |Dr. Anake, W. U

By

Dr. Anake W.U

1
 Covenant University
College of Science and Technology
Department of Chemistry

PROGRAMME: Industrial Chemistry

COURSE CODE: CHM 222
COURSE TITLE: Analytical Chemistry
UNITS: 3 Units
COURSE LECTURER: Dr. Anake, W. U.
SEMESTER: Omega
TIME: Wednesdays, 10 - 12 noon, Friday 12-1 pm
LOCATION: CST Building.

COURSE OUTLINE
Module 2 Volumetric methods of analysis
Week 4: Acid-base titrations, Oxidation-reduction titration
Week 5: Precipitation titration

TUTORIALS:
Tutorials will be given at the end of the course.
GROUND RULES & REGULATIONS
 Punctuality to classes
 No eating in the class

CHM 222_ Analytical Chemistry |Dr. Anake, W. U

 No sleeping & playing in class
 75% attendance required for eligibility to semester examination.
RECOMMENDED READING/TEXT
Gary, D. C. (2004). Analytical Chemistry (6th Ed). John Wiley and Sons, New York.
Douglas, A.S., Donald, M. W. and Holler, J. F. (1994). Analytical Chemistry an introduction (6th
Ed.). Saunders College Publishing, USA.
Mendham, J., Denney, R.C., Barnes, J.D and Thomas, M. (2004). Vogel’s Quantitative Chemical
Analysis (6th Ed.). Pearson Education Limited, India.
Harvey D. (2000). Modern Analytical Chemistry. McGraw-Hill Companies, New York, USA.

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 Volumetric Methods of Analysis

1.1 Introduction

Volumetric or titrimetric analysis is a general term for a method in quantitative chemical analysis
in which the amount of a substance is determined by the measurement of the volume that the
substance occupies. It is commonly used to determine the unknown concentration of a known
reactant.

A process in which a reagent of known concentration and volume (titrant) is used to react with
another substance of unknown concentration (titrand or analyte) until the reaction between the
analyte and titrant is judged to be complete is known as titration. An indicator is commonly used
in titration to locate the equivalence point. When titrating, acid can either be added to base or base
can be added to acid, both will result in an equivalence point, which is the condition in which the
reactants are in stoichiometric proportions. They consume each other, and neither reactant is in
excess.

The requirements for a successful titrimetric titration include:

(i) stoichiometric reaction: well defined reaction between titrant and analyte.
(ii) rapid reaction: reaction should have no side reaction, no interference from other foreign
substances.
(iii) indication of end of reaction: This indication include colour change, sudden increase in
pH, zero conductivity, etc.
(iv) known relationship between endpoint and equivalence point.

CHM 222_ Analytical Chemistry |Dr. Anake, W. U

Figure 1.1: Acid-base titration

1.1.1 Definition of Terms

 Standardization: this is a process in which the concentration of a solution is determined

by using the solution to titrate a known amount of another reagent

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  Titrant: the reagent added to a solution containing the analyte and whose volume is the
signal.
 Indicator: a coloured compound whose change in colour signals the end point of a
titration.
 Titration error: the determinate error in a titration due to the difference between the end
point and the equivalence point.
 Titration curve: the plot of pH versus volume.
 End point: the point at which the reaction is observed to be complete. It is the signal that
tells the analyst to stop adding reagent and make the final reading on the burette. Endpoint
is observed with the help of indicator
 Equivalent point: the point in which the amount of added titrant is chemically equivalent
to the amount of analyte in the sample. Since [H+] = [OH-] at the equivalence point, they
will combine to form the following equation:
H (aq )  OH (aq )  H 2O ,..(1)

This reaction results in the production of water, which has a neutral pH of 7.0. The pH at
the equivalence point is 7.0 because the solution only contains water and a salt that is
neutral. Since neither H+ nor OH- molecules remain in the solution, we can conclude that
at the equivalence point of a strong acid - strong base reaction, the pH is always equal to
7.0. Continuous addition of acid or base after reaching the equivalence point will lower or
raise the pH, respectively.

1.1.2 Methods for Expressing the Concentration of Solution

(i) Weight percent: weight percent is defined as the amount of solute in grams per 100
grams of solution.

CHM 222_ Analytical Chemistry |Dr. Anake, W. U

weight of solute
weight percent (w/w) = 100
weight of solution

(ii) Volume percent: volume percent is defined as the volume in mL of the solute per 100
mL of solution.

volume of solute
volume percent (v/v) = 100
volume of solution

(iii) Weight/volume percent: this is the amount of solute in grams per 100 mL of solution.

weight of solute, g
weight/volume percent (w/v)= 100
volume of solution, mL

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 (iv) Strength of solution: This is the number of grams of the solute per liter of solution.

weight of solute  g 
Strength of solution =
volume of solution  L 

(v) Molarity is defined as the number of moles of solute per liter of solution.

number of moles of solute

Molarity(M) =
volume of solution  L 

weight of solute
number of moles of solute (n) =
molecular weight

weight of solute
Molarity(M) =
molecular weight  volume of solution ( L)

strength of solution
Molarity(M) =
molecular weight

(vi) Normality is defined as the number of equivalents of solute dissolved in one liter of
solution

number of gram equivalent of solute

Normality (N) =
Volume of solution  L 

The number of equivalents of an acid or base can be determined from equivalent weight.

CHM 222_ Analytical Chemistry |Dr. Anake, W. U

Equivalent weight is defined as the molecular weight of the acid or base divided by the
number of replaceable hydrogen or hydroxyl ions.

weight of solute
equivalents of solute (n) =
equivalent weight

weight of solute
Normality(N) =
equivalent weight  volume of solution  L 

Parts per million (ppm) and part per billion (ppb) are used to describe the specific concentration
of very dilute solutions.

The term ppm is defined as the concentration of a solution in units of one part of solute to one
million parts solvent.

1 ppm = 1 milligram of solute per liter of solution.

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 ppm  mg L   g mL

Parts per billion (ppb), is defined as one part solute per one billion parts solvent. One ppb is equal
to one-microgram solute per liter of solution

ppb   g L  ng mL

1.1.3 Requirement for Successful Titrimetric Titration

(i) Stoichiometric reaction (well defined reaction between titrant and analyte).
(ii) Rapid reaction: Reaction should have no side reaction, no interference from other foreign
substances.
(iii)Indication of end of reaction, such as colour change, sudden increase in pH, zero
conductivity, etc.
(iv) Known relationship between endpoint and equivalence point.

1.2 Types of Volumetric Analysis

The various types of volumetric analysis include acid-base, precipitation, oxidation- reduction
titration and complexometric.
1.2.1 Acid-base Titration
When the reaction involves an acid and a base, the method is referred to as an acid-base titration.
 The types of acid-base titration include:
(i) Titration of strong acid with strong base.

CHM 222_ Analytical Chemistry |Dr. Anake, W. U

(ii) Titration of strong acid with weak base.
(iii)Titration of weak acid with strong base.
(iv) Titration of polyprotic acids.
 Choosing a titrant: In theory, any strong acid or strong base can be used as titrant. The
reason for this is that most reaction involving a strong acid or a strong base is
QUANTITATIVE.

Types of Acid & base Examples

Strong acid titrants Hydrochloric acid (HCl), nitric acid (HNO3), per chloric acid (HClO4),
phosphoric acid (H3PO4)
Weak acid titrants Acetic acid (CH3COOH), ammonium ion (NH4-), hydrogen fluoride (HF)
carbonic acid (H2CO3), nitrous acid (HNO2), hydrogen sulphide (H2S)
hydrogen cynide (HCN)
Strong base titrant Sodium hydroxide (NaOH), potassium hydroxide (KOH), magnesium hydroxide
(Mg(OH)2), barium hydroxide (Ba(OH)2)
Ammonium hydroxide (NH4OH), Carbonate(CO32-), Flouride ion (F-)
Weak base titrant
Sodium carbonate (NaCO3)

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1.2.1.1 Strong Acid - Strong Base Titrations

A strong acid-strong base titration determines the concentration of the acidic solution by titrating
it with a basic solution of known concentration, or vice-versa, until neutralization occurs. Hence,
the reaction is a neutralisation reaction. Strong acid-strong base have high values of Ka and Kb, as
such they fully dissociate (all the molecules of acid or base will completely separate into ions). At
the equivalence point, equal amounts of H+ and OH- ions will combine to form H2O, resulting in
a pH of 7.0 (neutral). The pH at the equivalence point for this titration will always be 7.0. This
holds only for titrations of strong acid with strong base. The anion (negative ion) created from the
dissociation of the acid combines with the cation (positive ion) created from the dissociation of
the base to form a salt.

Strong acid is an acid that is completely ionized in aqueous solution.

HA( aq )  H (aq )  A(aq )

Where H is hydrogen and A represents the conjugate base (anion) of the acid.

Strong base is a base that is completely ionized in aqueous solution.

XOH ( aq )  X (aq )  OH (aq )

Where OH is hydroxide and the X represents the conjugate acid (cation) of the base.

 Example of Strong Acid-Base Reaction

Reactions with strong acid and strong base, gives the same net ionic equation since the acid and
base completely dissociate as well as the resulting salt. The final product is water.

CHM 222_ Analytical Chemistry |Dr. Anake, W. U

1. The reaction between HCl and NaOH:

HCl( aq )  NaOH( aq )  H 2O(l )  NaCl( aq )

Since HCl and NaOH fully dissociate into their ion components, along with sodium chloride
(NaCl), we can rewrite the equation as:

H (aq )  Cl(aq )  Na(aq )  OH (aq )  H 2O(l )  Na(aq )  Cl(aq )

This equation can be simplified by eliminating the spectator ions and writing the net ionic
equation for this reaction

H   Cl( aq )  Na( aq

   
)  OH ( aq )  H 2O( l )  Na( aq )  Cl( aq )

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Net ionic equation:

H (aq )  OH (aq )  H 2O(l )

 Titration Curve of a Strong Acid - Strong Base Reaction

Titration curves are produced by monitoring the pH of a given volume of a sample solution
after successive addition of acid or alkali. The curves are usually plots of pH against the
volume of titrant added.

The pH curve diagram below represents the titration of a strong acid with a strong base:

NaOH ( aq )  HCl( aq )  NaCl( aq )  H 2O(l )

CHM 222_ Analytical Chemistry |Dr. Anake, W. U

Figure 1.2: pH curve of a strong acid with a strong base

As strong base is added to a strong acid, the pH increases slowly until it is near the equivalence
point, where the pH increases dramatically with a small increase in the volume of base added. This
is due to the logarithmic nature of the pH system (pH = -log [H+]). At the equivalence point, the
pH is 7.0, as expected. Passing the equivalence point by adding more base initially increases the
pH dramatically and eventually slopes off.

 pH and pOH calculations for strong acid-strong base titration

Example 1
What is the pH when 48.00 ml of 0.100 M NaOH solution is titrated with 50.00 ml of 0.100 M
HCl solution?

Solution

The net ionic equation is:

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 H (aq )  OH (aq )  H 2O(l )

The original number of moles of H+ in the solution is:

50.00 x 10-3L x 0.1 M HCl = 0.005 moles

The number of moles of OH- added is:

48.00 x 10-3L x 0.100 M OH- = 0.0048 moles

Which results in:

0.005-0.0048 = 0.0002 moles H+(aq)

The total volume of solution is 0.048L + 0.05L = 0.098L

[H+]= (0.0002/0.098L) = 2.0 x 10-3

pH= 2.69

Example 2
What is the pOH when 5.0 L of 0.45 M solution of sulphuric acid (H2SO4) is titrated with 2.3 L
of 1.2 M lithium hydroxide (LiOH) solution?

Solution

To solve this problem, first determine the moles of H  ions produced by the strong acid and the
weight of solute

CHM 222_ Analytical Chemistry |Dr. Anake, W. U

- 100
moles of OH ions produced by the strong base, respectively: weight of solution

Acid:

0.45 mol H2SO4 x 5.0 Liter 2 mol H+ = 4.5 mol H+

Liter 1 mol H2SO4

(Since a single mole of H2SO4 produces two moles of H2, it produces a ratio of (2 mol H+/ 1 mol
H2SO4)

Base:

1.2 mol LiOH x 2.3 Liter 1 mol OH- = 2.8 mol OH-
Liter 1 mol LiOH

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The moles of H+ are greater than the moles of OH-, find the moles of excess H+:

4.5 mol - 2.8 mol = 1.7 mol H+ in excess.

Since pOH = -log [OH-], first convert the moles of H+ in terms of molarity (concentration). Then
determine the concentration of OH- from the concentration of H+.

Total volume:

2.3 L + 5.0 L = 7.3 L

Using the total volume, calculate the molarity of H+:

1.7 mol H 
 0.23 M H 
7.3 L

Next, with molarity of H+, there are two ways to determine the pOH:

1. [H+][OH-] = 1 x 10-14

[0.23][OH-] = 1 x 10-14

[OH-] = 1 x 10-14 / 0.23 = 4.35 x 10-14

pOH = -log [OH-] = -log (4.35 x 10-14) = 13.4

2. pOH = 14 - pH

CHM 222_ Analytical Chemistry |Dr. Anake, W. U

= 14 - (-log [H+])

= 14 + log (0.23) = 13.4

The answer is 13.4 in both methods.

Example 3
Determine the pH at each of the following points in the titration of 30 mL of 0.05 M HCIO4 with
0.1 M KOH.
a. When no KOH is added; b. When 5 mL KOH is added; c. When 15 mL KOH is added

Solution

i.) Before adding any KOH

pH = -log[H+]

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Since initially there is 0.05 M HClO4, the pH is simply:

pH = -log [0.05 M]

pH = 1.30

ii.) When 5 mL of 0.1 M KOH is added

30 mL of 0.05 M HClO4 = (30 mL) x (0.05 M) = 1.5 mmol H+

5 mL of 0.1 M KOH = (5 mL) x (0.1 M) = 0.5 mmol OH-

First, write out the reaction between HClO4 and KOH:

HClO4( aq )  KOH( aq )  H 2O(l )  KClO4

= H (aq )  ClO4(aq )  K(aq )  OH (aq )  H 2O(l )  K(aq )  ClO4( aq )

Therefore net ionic equation = H (aq )  OH (aq )  H 2O(l )

Based on this equation:

1 mol HClO4 = 1 mol H+

1 mol KOH = 1 mol OH-
1 mol of H+ reacts with 1 mol OH-

CHM 222_ Analytical Chemistry |Dr. Anake, W. U

H  OH   H 2O
Initial (mmol) 1.5 1.5 
Change (mmol) -0.5 -0.5 
Final (mmol) 1 0 

We subtract 0.5 mmol from both because the OH- acts as the limiting reactant, leaving an excess
of 1 mmol H+.

Remember that:

Molarity = mmol/mL

Already mmol is given, so to find mL, add the volume of HClO4 and KOH:

Total Volume = mL HClO4 + mL KOH = 30 mL + 5 mL = 35 mL

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So,

Molarity of H+ = (1 mmol)/ (35 mL) = 0.029 M

pH = -log [H+] = -log[0.029]

pH = 1.54

Note: the pH is increasing as base is added

iii.) When 15 mL of 0.1 M KOH is added

30 mL of 0.05 M HClO4 = 1.5 mmol

15 mL of 0.1 M KOH = 1.5 mmol

H  OH   H 2O

Initial (mmol) 1.5 1.5 

Change (mmol) -1.5 -1.5 
Final (mmol) 0 0 

Remember that when [H+] = [OH-], this is the equivalence point.

At the equivalence point for a strong acid-strong base titration, the pH = 7.0

So, pH = 7.0

CHM 222_ Analytical Chemistry |Dr. Anake, W. U

1.2.1.2 Weak Acid-Strong Base Titrations

A weak acid will react with a strong base to form a basic (pH > 7) solution. A titration curve
reflects the strength of the corresponding acid and base, showing the pH change during titration.
The titration curve demonstrating the pH change during the titration of the strong base with a weak
acid shows that at the beginning, the pH changes very slowly and gradually. This indicates the
formation of a buffer system as the titration approaches the equivalence point.

At the equivalence point and beyond, the curve is typical of a titration of, for example, NaOH and
HCl. When the NaOH is in excess, the pH change is the same as in any system dominated by
NaOH.

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 Figure 1.3: pH changes during a titration of a weak acid with a strong base.

The initial pH of the solution at the beginning of the titration is approximately that of the weak
acid in water. At the equivalence point, all of the weak acid is neutralized and converted to its
conjugate base (the number of moles of H+ = added number of moles of OH–). However, the pH
at the equivalence point does not equal 7. This is due to the production of conjugate base during
the titration. The resulting solution is slightly basic. The endpoint and the equivalence point are
not exactly the same: the equivalence point is determined by the stoichiometry of the reaction,
while the endpoint is just the color change from the indicator.

Example: The titration of acetic acid (HC2H3O2) with NaOH.

HC2 H3O2  OH   H 2O  C2 H3O2

CHM 222_ Analytical Chemistry |Dr. Anake, W. U

During this titration, as the OH– reacts with the H+ from acetic acid, the acetate ion ( C2 H 3O2 ) is
formed. This conjugate base reacts with water to form a slightly basic solution.

C2 H3O2  H 2O  HC2 H 3O2  OH 

Volume of titrant (mL)

Figure 1.4: Weak acid-strong base titration curve showing equivalence point

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Example 4
What is the pH when 30.0 mL of 0.100 M NaOH is titrated with 50.0 mL of 0.100 M acetic acid?

Solution

STEP 1: Stoichiometric calculation:

The original number of moles of HC2H3O2 in the solution is:

50.0 x 10-3 L x 0.100 M = 5.00 x 10-3 moles HC2H3O2

Similarly, there are 3.00 x 10-3 moles of OH- due to the NaOH solution.

The reaction goes to completion:

OH ( aq )  HC2 H3O2( aq )  C2 H3O2( aq )  H 2O(l )

OH  HC2 H 3O2 C2 H 3O2

Initial (mol) 3.00  10-3 5.00  10-3 0

Change (mol) -3.00  10-3 -3.00  10-3 +3.00  10-3
Final (mol) 0 2.00  10-3 3.00  10-3

The total volume is 80.0 mL.

Calculate the resulting molarities:

CHM 222_ Analytical Chemistry |Dr. Anake, W. U

 2.00 103 mol HC2 H 3O2 
 HC2 H 3O2     0.0250 M
 0.0800 L 
 3.00 103 mol C2 H 3O2  
C2 H 3O2   

  0.0375 M
 0.0800 L 

STEP 2: Equilibrium calculation, using simplification:

 H   C2 H 3O2  
Ka      1.8 105
 HC2 H 3O2 
 H  
 K A  HC2 H 3O2 

1.8 10   0.0250 
5

 1.2 105 M
C2 H 3O2 

 0.0375
pH   log 1.2  105   4.92

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1.2.1.3 Strong Acid- Weak Base Titrations

A strong acid will react with a weak base to form an acidic (pH < 7) solution. Consider the reaction
between ammonia (a weak base) and hydrochloric acid (a strong acid) in the aqueous phase:

NH3( aq )  HCl( aq )  NH 4 ( aq )  Cl(aq )

When titrating the acid into the base for a strong acid-weak base titration, the pH of the base will
ordinarily start high and drop rapidly with the additions of acid. As the equivalence point is
approached, the pH will change more gradually, until finally one drop will cause a rapid pH
transition through the equivalence point. If a chemical indicator is used, methyl orange is a
preferable choice in this case. It changes from its basic to its acidic colour.

In strong acid-weak base titrations, the pH at the equivalence point is below 7. This is due to the
production of a conjugate acid during the titration; it will react with water to produce hydronium
( H 3O  ) ions.

For example, in the titration of HCl into ammonia solution, the conjugate acid formed (NH4+)
reacts as follows:

NH 4  H 2O  H3O  NH3

CHM 222_ Analytical Chemistry |Dr. Anake, W. U

Figure 1.5: pH change during titration of a strong acid with a weak base.

The curve depicts the change in pH (on the y-axis) vs. the volume of HCl added in mL (on the x-
axis)

Example 5

If 30.0mL of 0.200mol/L NH3 is titrated with 0.400mol/L HI, determine the pH of the solution at
the equivalence point. NH3 has a Kb of 1.76 x 10-5

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Solution

STEP 1: Write the equation of reaction:

NH3 ( aq )  HI ( aq ) NH 4 ( aq )  I ( aq )

0.200mol
No of mole of NH3 =  0.0300 L  0.00600 mol
L

NH3 HI NH4+ I-
Initial (mol) 0.00600 0.00600 0 
Change (mol) -0.00600 -0.00600 +0.00600 
Final (mol) 0 0 +0.00600 

Note: From the question, the concentration of HI is given, but no volume. Since NH3 and HI
reacts in a 1:1 molar ratio,

0.00600 mol of HI is needed to neutralize NH3. In addition, I- is a conjugate base of the acid
(HI), and HI is a strong acid, as such I- will have a negligible effect on the pH.

Solve for volume of HI added:

0.00600 mol
n  cv   0.0150 L
mol
0.400
L

Hence the new volume of the conjugate acid is (NH4+) = 0.0300L+0.0150L= 0.0450 L

CHM 222_ Analytical Chemistry |Dr. Anake, W. U

0.00600 mol
Concentration of the conjugate acid  NH4     0.133 mol / L
0.0450 L
K w 1.0 1014
Ka   5
 5.68 1010
Kb 1.76 10

K W  Ka  Kb

NH4+ H2 O NH3 H3 O+
I 0.133 mol/L   
C - X  +X +X
E 0.133-X  X X

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From the question, Kb of ammonia was given, but the Ka of acid is needed to solve the question.
However, since NH4+ is the acid we can solve for the Ka value by using the KW relationship,
K W  K a  K b ; where = K W  1.0 1014

K w 1.0 1014
Ka   5
 5.68 1010
Kb 1.76 10

The Ka value is used along with the equilibrium concentration from ICE table to solve for
 H 3O   .

First, write the Ka expression:

 NH 3   H 3O  
Ka 
 NH 4  

5.68  10 10 
 x  x 
0.133  x
Re arrange to generate a quadractic equation
7.55  10 11  5.68 10 10 x  x 2
 x 2  5.68  10 10 x  7.55  10 11  0
a b c
We can now use quadractic formulae to solve
5.68  10 10  b 2  4ac
x
2 1
x  8.69  10 6 or  8.70  10 6
ignore  8.70  10 6 , sin ce x is  H 3O   , as such we cannot have a negative concentration.

CHM 222_ Analytical Chemistry |Dr. Anake, W. U

 H 3O    8.69  10 6 mol / L
Hence pH   log  H 3O  
  log 8.69  10 6
 5.06

1.2.1.4 Titrations of Polyprotic Acids

Polyprotic acids have more than one ionisable proton. Examples are H2SO4, H3PO4, H2CO3, and
H2S. Except for sulphuric acid, the common polyprotic acids are all weak.
Points to note about polyprotic acids:
1. Polyprotic acids always dissociate in stepwise action. For example, H2CO3 neutralizes in
two steps:
H 2CO3 ( aq )  OH ( aq )  H 2O( l )  HCO3( aq )
HCO3 ( aq )  OH  ( aq )  H 2O(l )  CO32( aq )

17
 Figure 1.6: Polyprotic acid titration curve showing two equivalence points

2. The first H+ comes off much easier than the 2nd and 3rd and is denoted as Ka1, Ka2, Ka3. For
example

Polyprotic acid Ka1 Ka2 Ka3

Arsenic H3ASO4 5.6 10 3
1.0 107 3.0 1012

3. As long as the Ka value differ by a factor of 103 or more, it is possible to obtain a satisfactory
estimate of the pH of polyprotic acid solutions by considering only Ka1. Example, for
arsenic acid, Ka2 is significantly smaller than Ka1, its contribution to the pH of the system
is negligible. Hence, to calculate arsenic acid pH, only the first hydrogen ion with
dissociation constant is important to find the pH.

Example 6

CHM 222_ Analytical Chemistry |Dr. Anake, W. U

The solubility of carbon dioxide in pure water at 25oC and 0.1 atm pressure is 0.0037 M. All of
the dissolved gas is assumed to be in the form of carbonic acid.

(i) What is the equation for this reaction?

(ii) What is the pH of a 0.0037 M solution of carbonic acid? Ka1= 4.3E-7; Ka2= 5.6E-11

Solution

Equation of reaction: CO2 + H2O → H2CO3

The magnitude of Ka1 when compared to Ka2, meets the criteria of having the difference of 103 or
more. As such, the contribution of H+ from the 2nd is very insignificant as such Ka2 is not worth
measuring.

Ionic equation: H 2CO3 … H   HCO31 Ka1  4.3 107

18
 H 2CO3 … H   HCO31 K a1  4.3 107
0.0037 X X
2
X
4.3 107 
0.0037 M
7
 4.3 10  0.0037  X 2
4.3 107  0.0037  X 2
X   H    3.99 105
pH   log  3.99 105 
 4.40

1.3 Oxidation-Reduction Titration

Oxidation – reduction titration is one, which deals with a reaction involving oxidation and
reduction of certain chemical species. It is also defined as a titration based on an oxidation-
reduction reaction between an analyte and a titrant.

1.3.1 Definition of terms

Oxidation: refers to loss of electrons to give higher oxidation state. The electrode is always more
positive. For example: Na  Na   e

Reduction: refers to gain of electron to give lower oxidation state. The reduction electrode is
always more negative. For example: Cl  e  Cl

Oxidizing agent: is the substance(s) that gains an electron(s) and get reduced to lower oxidation
state.

CHM 222_ Analytical Chemistry |Dr. Anake, W. U

Reducing agent: is the substance(s) that tend to loss electron(s) and get oxidized to higher
oxidation state.

Oxidation number: This is a number that states the electrical charge possessed by each elemental
atom in the molecular compound or the ion.
Oxidation State: oxidation state is the “charge” an atom of an element would have if it existed as
an ion in a compound (even if it is actually covalently bonded).

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Oxidant and Reductant

1.3.2 A Special Redox: Disproportionation

A disproportionation reaction is a redox reaction in which one species is simultaneously oxidised
and reduced.
Cl2  2OH    ClO   Cl   H 2 O
0 1 1

Chlorine is simultaneously reduced from oxidation state of 0 in Cl2 to -1 in Cl-, and oxidised from
oxidation state of 0 in Cl2 to +1 in ClO- (hypochlorite).

Not All Reactions are Redox Reactions

Reactions in which there has been no change in oxidation number are NOT redox reactions.

Example

CHM 222_ Analytical Chemistry |Dr. Anake, W. U

1 5 2 1 1 1 1 1 5 2
Ag N O3 (aq)  Na Cl (aq)  Ag Cl ( s)  Na N O3 (aq)

1 2 1 1 6 2 1 6 2 1 2
2 Na O H (aq)  H 2 S O 4 (aq)   Na 2 S O 4 (aq)  H 2 O(l )

1.3.3 Determination of End Point in Oxidation Reduction Titration

The end point in a redox titration can be identified with the following:
(i) Indicator electrode - electrical measurement, such as the potential of the solution.
(ii) Redox indicators - the indicator has different colour at reduction and oxidation state.
(iii)Non-redox indicator - changes colour when excess amount of titrant exists, e.g. Starch
changes to deep blue colour when excess amount I2 remains.

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  Redox Indicators

 Redox Reaction involving Iodine

The oxidation-reduction reactions, which involve the use of iodine, are classified as follows:
(i) Iodimetry (direct method)
This is when a reducing analyte (e.g. S2O32-, Sn2+, ……etc) is titrated directly with iodine.
(ii) Iodometry (indirect method)
Iodometry refers to the addition of oxidizing analyte (e.g. IO3-, Cr2O72-, MnO4-, H2O2 …….etc)
to excess iodide (I-) to produce iodine, which is then titrated with standard thiosulphate solution.
Sodium thiosulfate is the most widely used reducing agent and is historically associated with
titrations involving iodine.
Iodine is very slightly soluble in water but is readily soluble in water containing iodide ion due to
the following equilibrium
Cu 0 ( s)  Cu 2 (aq)  2e 

The triiodide is the oxidizing agent involved in iodometric and iodimetric titrations. A mild

CHM 222_ Analytical Chemistry |Dr. Anake, W. U

oxidizing agent can be efficiently used in redox titrations, provided enough precautions are
considered.s

Indicator for Iodine

The most widely accepted indicator in iodine titrations is starch.
 Starch responds to iodine not to a change in potential.
 It is readily biodegradable and must be freshly prepared.
 Starch forms a complex with iodine leading to a deep blue colour.
 Starch is added near the end point in iodometry, but at the beginning for iodimetry.

1.3.4 Methods for Balancing Redox Equation

The two methods are:
(i) Oxidation-number changes
This method works well if the oxidized and reduced species appear only once on each side of the
equation, and there are no acids or bases.
(ii) Half-reactions

21
The half-reaction method works best for reactions taking place in acidic or alkaline solution.

 Balancing Redox Equation

(i) Balancing simple redox reactions

Cu (s) + Ag + (aq) Ag(s) + Cu2+(aq)

Step 1: Pick out similar species from the equation

Cu(s) Cu2+ (aq)
Ag +(aq) Ag (S)
Step 2: Balance the equations individually for charges and number of atoms
Cu 0  S  Cu 2  aq   2e 
Ag   aq   e  Ag S
Cu 0 S  Cu 2  aq   2e
Cu0(S) becomes Cu 2+ (aq) by loosing 2 electrons.
So Cu0(S) is oxidized to Cu2+ (aq) resulting in the oxidizing half reaction.
Ag   aq   e  Ag S
Ag+ (aq) becomes Ag 0 (S) by gaining 1 electron.
So Ag+(aq) is reduced to Ag (S) resulting in the reducing half reaction.

Final Balancing:
Making the number of electrons equal in both
half reactions

CHM 222_ Analytical Chemistry |Dr. Anake, W. U

Cu 0  S  Cu 2  aq   2e    1
 
 Ag  aq   e  Ag S    2
 

So we have,
Cu 0  S  Cu 2  aq   2e 
2Ag   aq   2e   2Ag S 

Cu0(S) +2Ag + (aq) + 2e- Cu2+(aq) + 2Ag (S) + 2 e-

Cu 0 (S)  2Ag  (aq)  Cu 2 (aq)  2Ag S
Number of e-s involved in the overall reaction is 2

22
 (ii) Balancing complex redox reactions

Balance this redox equation:

Fe+2(aq) + MnO4-(aq) Mn+2(aq) + Fe+3(aq)

Solution

Fe2+ (aq) + MnO4-(aq) Mn2+ (aq) + Fe3+ (aq)

Oxidizing half : Fe2  aq   Fe3  aq   1e

Reducing half : MnO4 (aq)  Mn2 (aq)
Balancing atoms :
Balancing oxygens : MnO4   aq   Mn2  aq   4 H 2 O
Balancing hydrogens:
Reaction happening in an acidic medium
MnO4  aq   8H  Mn2  aq   4H 2 O
 

Oxidation numbers: Mn = +7,

O = -2 Mn = +2
Balancing electrons:
The left side of the equation has 5 less electrons than the right side
MnO4   aq   8H   5e  Mn 2  aq   4 H 2 O
Reducing Half
Final Balancing:
Making the number of electrons equal in both half reactions

CHM 222_ Analytical Chemistry |Dr. Anake, W. U

 Fe2 (aq)  Fe3  aq   1e   5
[MnO4   aq   8H   5e  Mn 2  aq   4 H 2 O]  1

5Fe2 (aq)  5Fe3  aq   5e

MnO4   aq   8H   5e  Mn 2  aq   4 H 2 O

5Fe2  MnO4  aq   8H   5e 5Fe3  Mn 2  aq   4H 2 O  5e

5Fe2  MnO4 (aq)  8H  5Fe3  Mn 2 (aq)  4H2 O

5 Fe 2+ ions are oxidized by 1 MnO4- ion to 5 Fe3+ ions. Conversely, 1 MnO4- is reduced by 5 Fe2+
ions to Mn2+. If we talk in terms of moles: 5 moles of Fe 2+ ions are oxidized by 1mole of MnO4-
ions to 5 moles of Fe3+ ions. Conversely, 1 mole of MnO4- ions is reduced by 5 moles of Fe2+ ions
to 1 mole of Mn2+ ions.

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1.4 Precipitation Titration

This is the titrations between analytes and reagents resulting in the formation of an insoluble
precipitate. For example:
AgNO3 (aq) + NaCl (aq) → AgCl(s) + NaNO3 (aq)
Ionic equation: Ag+ + Cl- → AgCl
Examples of solutions used in precipitation titrations include:

 Silver nitrate (AgNO3), the most widely used precipitating reagent: for titration of Br-,CI-,
I- and CN
AgCl s   Ag   aq   Cl  aq 
 Potassium cyanate (KCN): for titration of Cu and Ni.

 Mercury(II) nitrate (Hg(NO3)2: for titration of Cu, CI-, Br-, I- and SCN
The reaction used in precipitation titration must satisfy a number of conditions:
• The precipitate must be practically insoluble
• Precipitation should be rapid
• End point (equivalence point) must be easily detected.

1.4.1 Solubility product:

For sparingly soluble salts, when placed in water, an equilibrium is established when the rate of
dissolution of ions from the solid equals the rate of precipitation of ions from the saturated solution.

AgCl s   Ag  aq   Cl  aq 

CHM 222_ Analytical Chemistry |Dr. Anake, W. U

 Ag  
 Cl 


The equilibrium constant K c is: Kc   

 AgCl 
Since the concentration of pure solid is constant
 Kc  AgCl   
 Ag 

 
 Cl 


 K sp 
 Ag 

 Cl 


Where Ksp is the solubility product constant.

Example 7

The solubility of silver chloride is 0.0015 g per L. Calculate the solubility product.

24
The relative molecular mass of silver chloride is 143.3.
0.0015
The solubility is therefore  1.05 10 5 mol per L.
143.3
In a saturated solution, 1 mole of AgCl will give 1 mole each of Ag + and Cl -
Hence [Ag + ] = 1.05 x 10-5 and [Cl - ] = 1.05 x l0 -5 mol L-1.
K sp = [Ag + ] [Cl- ] = (1.05 x l0-5 ) x (1.05 x l0 -5 )
 1.1 x l0-10

1.4.2 Methods for Determination of End Point in Precipitation Titration

This can be obtained using chemical indicators (Mohr, Volhard and Fajans’method) and sensors
such as potentiometric and amperometric.
(i) Chemical Indicator for Precipitation Titrations
Three methods for the determination of precipitation titration with visual indicators include:
 Mohr method for determining chloride
This method depends on the formation of a coloured precipitate. Chromate ion acts as an indicator
in this method. Chloride is titrated with AgNO3 solution. A soluble chromate salt is added as the
indicator. This produces a yellow colour solution. A white precipitate of silver chloride is formed,
as it is less soluble than silver chromate.
Ag   Cl   AgCl s   white 

At the end point where all the chloride ions are consumed, the first drop of Ag+ in excess will react
with the chromate indicator giving a reddish or light brown silver chromate precipitate.
2 Ag   CrO42 Yellow  Ag2CrO4  Re d 
This technique, is called argentometry and can be used for determination of halides (Cl-, Br-, I-),

CHM 222_ Analytical Chemistry |Dr. Anake, W. U

mercaptans (thioalcohols), fatty acids and several divalent anions.
N/B: In this method, the pH of solution is maintained at about 7. This is because, in alkaline
solutions, Ag will react with the OH ions forming AgOH while in acidic solutions; chromate will
be converted to dichromate.

Example 8
Find the concentration of chloride in a 25 mL solution to which few drops of K2CrO4 were added,
if the end point required 20 mL of 0.10 M AgNO3.
Solution
Ag+ + Cl– → AgCl(s)

The reaction between silver ions and chloride is 1:1

mmol Ag+ = mmol Cl-
0.10 x 20 = MCl- * 25
MCl- = 0.08 M

25
  Volhard Method
This is an indirect titration procedure for the determination of anions that precipitate with silver
like Cl-, Br-, I-, SCN-, and it is preferred in acidic (HNO3) solution. A measured excess of AgNO3
is added to precipitate the anion, and the excess of Ag+ is determined by back titration with a
standard solution of potassium thiocyanate.
Ag+(aq) +Cl–(aq) → AgCl(s) + excess Ag+
excess Ag+(aq) + SCN–(aq) → AgSCN(s)
Iron (III) serves as the indicator. The end point is detected by adding iron III (Fe3+) as ferric
ammonium sulphate, which forms a soluble red complex with the first slight excess of thiocyanate
ion
Fe3+ (aq) + SCN–(aq) → [FeSCN]2+(aq)

The titration occurs in acidic solution to avoid precipitation of Iron (III) as hydrated oxide.

Example 9
The % w/w I– in a 0.6712-g sample was determined by a Volhard titration. After adding 50.00
mL of 0.05619 M AgNO3 and allowing the precipitate to form, the remaining silver was back
titrated with 0.05322 M KSCN, requiring 35.14 mL to reach the end point. Report the % w/w I–
in the sample.

Solution
Conservation of charge for this back titration requires that
Moles Ag+ = moles I– + moles SCN–
Making appropriate substitutions for moles of Ag+, I–, and SCN– leaves us with
gI 
M AgVAg   M SCNVSCN
AWI 

CHM 222_ Analytical Chemistry |Dr. Anake, W. U

gI    AWI    M AgVAg  M SCNVSCN 
 0.1192 g

Solving for the grams of I–, we find

gI    AWI    M AgVAg  M SCNVSCN 

 0.1192 g

that there is 0.1192 g of iodide. The weight percent iodide, therefore, is

0.1192 g
100 17.76 % w w I 
0.6712 g

26
  Fajans method

It involves the use of adsorption indicators. An adsorption indicator is an organic compound that
tends to be adsorbed on to the surface of the solid in a precipitation titration. Example of adsorption
indicators include, acid dyes such as fluorescein and eocine and basic dyes like rhodamine.
Consider the titration of Cl- with Ag+. Before the end point the excess of Cl ions causes the
colloidal AgCl to have a negative charge. The indicator has a negative charge so it is repelled by
the colloidal particle.

After the end point the slight excess of Ag+ causes the colloidal AgCl to have a positive charge,
which attracts the negatively charged indicator. The free indicator has a different colour than the
adsorbed indicator.

AgCl : Ag+ : : indicator-

The colour of the adsorbed indicator is different from that of the un-adsorbed indicator, and this
difference signals the completion of the titration. Increased acidity decreases the degree of
adsorption of the indicator. The endpoint is observed by a change in colour from fluorescent
green to light pink.

CHM 222_ Analytical Chemistry |Dr. Anake, W. U

Figure 1.7: Colour change with adsorption indicators

27