Philippine Handbook Analytical Chemistry

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B3. ANALYTICAL CHEMISTRY

This branch of chemistry involves the study of separation, identification and composition of
matter. It is divided into two: quantitative analysis and qualitative analysis. Qualitative
analysis involves identification of the components of a given sample while quantitative
analysis deals with the determination of the proportions at which the components are present.

B3.1. METHODS OF ANALYSIS

In quantitative analysis, methods are classified as classical and modern methods. Classical
methods include gravimetric methods and volumetric methods. Modern methods are
instrumental methods like electroanalytic and spectroscopic methods.

Gravimetric analysis involves the determination of weight of the substance chemically related
to it. Volumetric analysis deals with the volume of the solution that is chemically equivalent to
the analyte.

Electroanalytic methods, on the other hand, measure the electrical properties of the sample
such as current, potential difference, and resistance. Spectroscopic methods relate the
production of electromagnetic radiation of analytes or their interactions.

A typical analysis starts with the search for an appropriate method that will satisfy the need
for an accurate and economical one. Standard analyses can be obtained from published
journals like Association of Official Analytical Chemists (AOAC). After the method selection,
sampling is done. A laboratory sample is obtained in such a way that it represents the entire
bulk sample. Physical treatment like grinding and crushing is done to the sample to attain a
size fit for the laboratory. Replicate samples are also prepared to ensure reliability of the
analysis. Commonly, analyses are done in solutions. The most common solvent is water. If the
sample is sparingly soluble, acids, bases and fluxing agents in varying concentrations and
application of heat are used to completely dissolve the sample. In most of the samples, some
substances are present that interferes in the analysis. Precipitation and masking are usually
employed to eliminate such interferences. After these substances are removed, measurement
of the analyte is done based on the methods described. Statistical methods are then finally
applied to the data obtained to check on the accuracy and precision of data.

B3.1.1. Gravimetric Analysis

Gravimetric method deals on mass measurement. One type of gravimetric analysis is

precipitation method. In this method, the analyte is converted into a sparingly soluble
precipitate by the addition of a precipitating agent. The precipitate is then filtered, washed and
converted into a product of known composition and weighed. Another type is volatilization
method. In this method, the analyte decomposes and the lost of mass of the sample indicates

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the amount of product that is chemically related to the analyte. In some cases, the
decomposition product is collected or absorbed and then weighed.

The percentage of the analyte by mass in the sample can be computed using the gravimetric
factor, (GF):

substance weighed  GF
% wt analyte  100%  (B3 – 1)
mass of sample
Molar Mass of desired substance (ds) x ds
GF   (B3 – 2)
Molar Mass of substance weighed (sw) y sw

A. Precipitation Method

In dealing with this method, a precipitating agent must be properly selected so that the
precipitate obtained is easily filtered, inert towards the atmosphere and of known composition
after drying or application of a suitable heat treatment. Table B3 – 1 lists the common
inorganic and organic precipitants.

Table B3 – 1. Common Organic and Inorganic Precipitants.

Precipitant Element(s) Precipitated Weighed Form
Al Al2O3
NH3 Fe Fe2O3
Cr Cr2O3
Mg Mg2P2O7
(NH4)2HPO4
Zn Zn2P2O7
H2PtCl6 K K2PtCl6
Cl AgCl
AgNO3 Br AgBr
I AgI
=
BaCl2 SO4 BaSO4
Nickel
dimethylglyoxime Ni
dimethylglyoxime
K+ KB(C6H5)4
NaB(C6H5)4 +
NH4 NH4B(C6H5)4

B3.1.2. Volumetric Analysis

This method involves the measurement of the volume that will react with the analyte
completely. A standard solution is used to titrate the sample. A standard solution is a solution
of known concentration. Methods of expressing concentrations of solutions are discussed in
section B1.3.3. For a standard solution, it must be stable, reacts rapidly and completely with

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the analyte and its reaction with the analyte can be described by a simple chemical equation.
The concentration of a standard solution is done by standardization using a primary standard.
A primary standard is a compound of high purity, stable towards air, soluble in water and
readily available at a reasonable cost. In this section, acid-base, precipitation, complex
formation, and oxidation-reduction titrations are discussed with its applications.

A. Acid-Base Titration

Neutralization reaction is a reaction between an acid and a base to form salt and water. The
reaction is almost complete and can be represented through a simple chemical equation.
Definitions of acids and bases are given in Table B3 – 2.

Table B3 – 2. Definitions of Acids and Bases.

DEFINITIONS ACIDS BASES
+
Produces H3O Produces HO– ions
Arrhenius
ions in solution in solution
Bronsted–Lowry Proton donor Proton acceptor
Electron – pair Electron pair
Lewis
acceptor donor

Acids and bases can be classified according to the number of replaceable hydronium ions or
equivalent hydroxide ions or according to their extent of ionization or dissociation in water.
Strong acids/bases ionize completely in water while weak acids/bases partially ionize in
water. Table B3 – 3 summarizes this classification.

Table B3 – 3. Classification of Acids and Bases According

to Extent of Ionization.
ACIDS BASES
HCl HNO3
Bases of Group 1A
Strong HBr HClO4
and Group 2A
HI H2SO4*
HNO2 HCN
NH3 and
Weak HF Organic
derivatives
H2SO3 acids

Table B3 – 4. According to Number of Replaceable Hydronium

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Ion and Equivalent Hydroxide Ion.

ACIDS BASES
Monoprotic / HNO3 HCN LiOH NH3
Monoequivalent HCl CH3COOH NaOH CH3NH2
Diprotic / H2SO4 H2C2O4 Ba(OH)2
Mg(OH)2
Diequivalent H2CO3 H2C4H4O6 Ca(OH)2
Polyprotic / H3PO4
H3AsO4 Al(OH)3
Polyequivalent H3PO3

1. Strength of Acids and Bases

The strength of an acid and a base is measured through its pH. When the acid is the major
contributor of the hydronium ion (H3O+) in solution, the pH can be calculated as


pH  log H 3O   (B3 – 3)

For alkali solutions, the pOH can be a measure of its strength and is computed as

pOH  log HO    (B3 – 4)

For solutions at 25C, the pH and pOH are related as follows:

pH  pOH  14 (B3 – 5)

The ionization reactions of acids and bases are summarized as follows:

HCl + H2O  H3O+(aq) + Cl–(aq) strong acid

HCN + H2O  H3O+(aq) + CN–(aq) weak acid
NaOH + H2O  Na+(aq) + HO–(aq) strong base
NH3 + H2O  NH4+(aq) + HO–(aq) weak base

Note that for strong acids and bases, reaction goes to completion and the concentration of the
acid or base is equal to the concentration of the hydronium or hydroxide ion. For weak acids
and bases, the extent of ionization is given by their ionization constant, KI. Table B3 – 5
shows the ionization constant of common weak acids and bases.

Table B3 – 5. Ionization Constant of Common Weak Acids and Bases at 25C.

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ACID KA BASE KB
Acetic Acid 1.75  10 –5
Ammonia 1.75  10–5
Benzoic Acid 6.28  10–5 Aniline 3.98  10–10
Formic Acid 1.80  10–4 Methyl amine 4.35  10–4
Hydrogen cyanide 6.2  10–10 Dimethyl amine 5.95  10–4
Hydrogen fluoride 6.8  10–4 Trimethyl amine 6.33  10–5
Nitrous acid 7.1  10–4 Hydrazine 9.52  10–7

The pH of acids and bases can be computed using the following equations:

Strong Acid pH  log C acid  (B3 – 6)

 K 2  4K C 
acid  K A
Weak Acid pH  log  A A
 (B3 – 7)
 2 
 
Strong Base pH  log n OH C base  (B3 – 8)
 K 2  4K C 
base  K B
pH  14  log  
B B
Weak Base (B3 – 9)
 2 
 

The extent of ionization can also be expressed in terms of percentage ionization:

% ionization 
H O  or HO   100%
3
 -

(B3 – 10)
 C acid  or  C base 
Based from the equations presented, the higher the ionization constant, the more acidic or
alkaline the solution is and therefore the higher the percentage ionization. It is also important
to note that pH is applicable to dilute solutions of acids and bases and the logarithmic function
is used solely for convenience thus avoiding very small number expressed in scientific
notation. For acids greater than 1M, the pH is not anymore applicable. Since the logarithm of
real numbers greater than one is positive, the pH value that can be obtained is negative.

2. Standardization of Acids and Bases

Titrimetric methods of analysis measure the volume of solutions of known concentration that
is chemically equivalent to the analyte in the sample. Standardization is the process of such
concentration determination. For acids and bases, several primary standards are being used
that are obtained in such a high purity, greater extent of solubility in water, high molecular
weight and very stable towards air. Table B3 – 6 presents the primary standards used for acids
and bases.

Table B3 – 6. Primary Standards Used for Standardization of Acids and Bases.

ACID BASE

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Sodium Carbonate, Na2CO3 Potassium Hydrogen Phthalate (KHP)

O- K+
+
Na O-

+ -
O C Molar Mass = 106 Molar Mass = 204.22
Na O C
HO C
COCH3–2+2H3O+ 3H2O+CO2
O
C C CH

Tris-hydroxylmethylamino
O HC CH methane
OH
Sulfamic Acid, HSO3NH2
H2C
Molar Mass = 121
O
H2C C NH2

HO
HO S NH2 Molar Mass = 97.09
H2C
OH
O
Mercuric Oxide, HgO Benzoic Acid, C6H5OH
HO HC CH

Hg ++
O--2 Molar Mass = 122.12
C C CH
Molar Mass = 216.59
O CH HC
HgO + 4I– + H2O  HgI4–2 + 2HO–
HO–+ H3O+  2H2O
Oxalic acid, H2C2O4
O
Sodium Tetraborate Decahydrate
C OH
Molar Mass = 90
HO C
Na2B4O7 . 10H2O
Molar Mass = 381
B4O7O–2 + 2H3O+ + 3H2O  4 H3BO3
H2C2O4 + 2HO–  C2O4–2 + 2H2O

Note: Primary standards listed reacts in 1:1 ratio with an acid or base otherwise reaction is specified.

3. Indicators for Titration, Titration Curves and Buffer Solutions

When the standard solution added is chemically equivalent to the analyte in the sample, the
equivalence point is attained. Such point in the reaction is detected using an indicator. These
indicators are consisting of weak organic acid or base whose undissociated form has different
color with its conjugate. The point at which there is an observable change in the solution due
to color change of the indicator is known as end point.

Table B3 – 7. Acid–Base Indicators.

ACID TYPE

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pH Color
Name
Transition Range Change
Bromothymol blue 6.2 – 7.6 yellow to blue
Phenolphthalein 8.3 – 10.0 colorless to pink
Bromocresol green 3.8 – 5.4 yellow to blue

BASE TYPE
Methyl orange 3.1 – 4.4 red to yellow
Methyl red 4.2 – 6.3 red to yellow
Methyl yellow 2.9 – 4.0 Red to yellow

When the acid reacts completely with the base, salt and water is formed. The nature of the salt
dictates the pH of the solution thus the indicator to be used for titration.

At equivalence point, only the salt is responsible for the relative acidity or alkalinity of the
solution. For titration of a strong acid with a strong base, the pH at equivalence point is 7 or
neutral. A concrete example is the titration of HCl and NaOH.

HCl + NaOH  NaCl + H2O

For titration of a weak acid with a strong base, the salt formed is basic and therefore the pH at
equivalence point is greater than 7. Titration of acetic acid with sodium hydroxide is a typical
example.
CH3COOH + NaOH  CH3COONa + H2O
(pH at equivalence point > 7.0)

When the salt is formed, it may undergo hydrolysis. As a general rule, salt coming from weak
acids or weak bases hydrolyzes in water. For sodium acetate, the hydrolysis reaction is

CH3COO– + H2O  CH3COOH + HO–

The pH at equivalence point can be calculated as:

 K 2  4K C  K 
pH  14  log  h h salt h
 (B3 – 11)
 2 
 
K W 110 14
Kh   , hydrolysis constant (B3 – 12)
KA KA

For titration of a weak base with a strong acid, the resulting solution is acidic. Titration of
ammonia with HCl gives the reaction:

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HCl + NH3  NH4Cl

The hydrolysis reaction for NH4Cl is

NH4+ + H2O  H3O+ + NH3

The pH of the solution is calculated as follows:

 K 2  4K C  K 
pH  log  
h h salt h
(B3 – 13)
 2 
 

The titration of weak acid with a weak base is not commonly used in volumetric analysis.
This is because there is no sharp endpoint observed and no indicator can be used to signal the
end of titration. However, the pH at equivalence point can be calculated using the equation:

 KWKA 
pH   1 2 log   (B3 – 14)
 KB 

For the reaction,

NH4OH + CH3COOH  NH4OOCCH3 + H2O

The ionization constants for acetic acid and ammonia are used to calculate the pH at
equivalence point and KW is the ionization constant for water at 25C having a value of 1 x
10–14. The self-ionization or autoprotolysis of water is given by the reaction:

H2O + H2O  H3O+ + HO–

Titration curves are being used to identify the indicator fit for a given combination of acids
and bases. Figures B3 – 1 and B3 – 2 are examples of titration curves.

Titration Curve of 0.1 M CH3COOH with 0.1 M NaOH

14
13
12
11
10
9
8
pH

7
6
5
4
3
2
1
B3 - 8
0
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56 58 60

Volum e of Base Added

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Figure B3 – 1. Titration Curve of Acetic Acid.

Titration Curve of 0.1 M HCl with 0.1 M NaOH

14
13
12
11
10
9
8
pH

7
6
5
4
3
2
1
0
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56 58 60

Volum e of Base Added

Table B3 – 2. Titration Curves OF HCl.

Note that in the titration of a weak acid with a strong base, a region wherein the addition of
base has a little effect on the pH of solution. This region is known as the buffer region. In this
region, the solution contains the unreacted weak acid and its conjugate salt. The solution
formed is known as buffer solution. At this point in titration, the pH of the buffer solution
formed can be computed using the Henderson–Hasselbach Equation given as follows:
pH  pK A  log
 acidic component
(B3 – 15)
 basic component

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If a buffer solution containing a weak base and its conjugate salt is present, pK A can be
obtained using the relationship:

KW
KA  (B3 – 16)
KB

4. Applications of Acid–Base Titration

Kjeldahl Method. This method is used to determine organic nitrogen content of samples and
can be extended for protein determination. The following steps are followed for this analysis:

1. Digestion. The sample is oxidized in hot, concentrated sulfuric acid, H2SO4 and
turns black. This step is necessary to convert carbon and hydrogen to CO 2 and
H2O, amides and amines to NH4+ and azo, azoxy and nitro group to N or its oxides.
Potassium Sulfate (K2SO4) is also used to increase the boiling point of sulfuric acid
and Mercuric Oxide (HgO) as promoter.

2. Distillation. The oxidized solution is cooled and treated with NaOH to liberate
ammonia gas according to the reaction: NH4+ + HO-  NH3(g) + H2O

3. Titration. Ammonia due to its high volatility can be collected in two ways:

i. Using an excess amount of hydrochloric acid, HCl. The NH3 liberated from the
sample is collected in an excess amount of standard HCl solution and the
excess is determined by a standard NaOH solution using methyl red indicator.
This type of titration is called back titration. The amount of nitrogen in the
sample is calculated as:

  1 mol HCl  1 mol NH 3 1 mol N 14.07 g N

g N   M HCl  VHCl    M NaOH  VNaOH      
(B3 – 17)
  1 mol NaOH  1 mol HCl 1 mol NH 3 1 mol N

ii. Using an excess amount of boric acid, H 3BO3. Ammonia is collected in an

excess amount of boric acid solution. The reaction is

NH3 + H3BO3  NH4+ + H2BO3-2

The reaction of ammonia with boric acid produces a strong conjugate base,
H2BO3-2 that is titrated by a standard HCl solution. This type of titration is
called replacement titration. The nitrogen content of the sample is determined
by the equation:
-2
1 mol H 2 BO 3 1 mol NH 3 1 mol N 14.07 g N
g N   M HCl  VHCl    -2
  (B3 – 18)
1 mol HCl 1 mol H 2 BO 3 1 mol NH 3 1 mol N

To get the nitrogen content of the sample,

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gN
% N wt   100% (B3 – 19)
g sample

The protein content of the sample can also be calculated using the following factors:

% CHON = % N * f (B3 – 20)

where f = 6.25 for meat products

f = 6.38 for dairy products
f = 5.70 for cereals

Double–Indicator Titration. One interesting application of neutralization titration is the

quantitative and qualitative of mixture of acids and bases.

Mixture of Bases. These samples contain sodium carbonate, sodium hydroxide and sodium
bicarbonate, either alone or in compatible combinations. In this method, the sample is titrated
with standard HCl to the phenolphthalein endpoint. When the solution becomes colorless,
methyl red is added and titrated until the solution turns salmon pink. Table B3-8 shows the
variation of volume for two endpoints and the corresponding components of the mixture.
Table B3 – 8. Mixture of Bases Using Phenolphthalein
and Methyl Red.
COMPONENT VOLUME OF TITRANT
Na2CO3 and NaOH *V0-Ph > VPh-MR
Na2CO3 and NaHCO3 V0-Ph < VPh-MR
NaOH only VPh-MR = 0
Na2CO3 only V0-Ph = VPh-MR
NaHCO3 only V0-Ph = 0
* All volume terms used in this text are in liters (L)

For a mixture of Na2CO3 and NaOH, the percentage of each component in the sample is
calculated using the following equations:
1 mol Na 2CO3 106.00 g Na 2CO3
2 VPh MR  ( M HCl )  
2 mol HCl 1 mol Na 2CO3 (B3 – 21)
% Na 2 CO3   100%
mass of sample (gram)
 V0Ph - VPh MR  (M HCl )  1 mol NaOH  40.00 g NaOH
% NaOH  1 mol HCl 1 mol NaOH  100% (B3 – 22)
mass of sample (gram)
For a mixture of Na2CO3 and NaHCO3, percentage composition of the sample is calculated
using the following equations:

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1 mol Na 2 CO 3 106.00 g Na 2 CO 3
2 V0Ph  M HCl   
2 mol HCl 1 mol Na 2 CO 3 (B3 – 23)
% Na 2 CO 3  100%
mass of sample (gram)
 VPh MR - V0Ph  M HCl   1 mol NaHCO3  84.01g NaHCO3
1 mol HCl 1 mol Na 2CO3 (B3 – 24)
% NaHCO 3  100%
mass of sample (gram)

For samples containing NaOH, Na2CO3 or NaHCO3, the amount of each component in weight
percentage is given as follows:

 V0Ph  M HCl   1 mol NaOH  40.00 g NaOH

% NaOH  1 mol HCl 1 mol NaOH  100% (B3 – 25)
mass of sample (gram)

 VPh MR  M HCl   1 mol NaHCO3  84.01 g NaHCO3

1 mol HCl 1 mol Na 2 CO 3 (B3 – 26)
% NaHCO3  100%
mass of sample (gram)

1 mol Na 2 CO 3 106.00 g Na 2 CO 3
2 V0Ph  M HCl   
2 mol HCl 1 mol Na 2 CO 3 (B3 – 27)
% Na 2 CO 3  100%
mass of sample (gram)

In some procedures, duplicate samples are titrated with standard HCl, one with
phenolphthalein indicator and the other sample with bromocresol green. Table B3 – 9 shows
the volume at phenolphthalein and bromocresol green endpoint for sample of mixture of
bases.

Table B3 – 9. Mixture of Bases Using Phenolphthalein and

Bromocresol Green.
COMPONENT VOLUME OF TITRANT
Na2CO3 and NaOH V0-Ph > ½ V0-BCG
Na2CO3 and NaHCO3 V0-Ph < ½ V0-BCG
NaOH only V0-Ph = V0-BCG
Na2CO3 only V0-Ph = ½ V0-BCG
NaHCO3 only V0-Ph = 0

The amount of the components are calculated as follows:

Mixture of Na2CO3 and NaOH

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1 mol Na 2 CO3 106.00 g Na 2 CO3

2 V0BCG - V0Ph  (M HCl )  
2 mol HCl 1 mol Na 2 CO3 (B3 – 28)
% Na 2 CO3  100%
mass of sample (gram)
 2V0Ph - V0BCG  (M HCl )  1 mol NaOH  40.00 g NaOH
% NaOH  1 mol HCl 1 mol NaOH  100% (B3 – 29)
mass of sample (gram)

Mixture of Na2CO3 and NaOH

1 mol Na 2 CO 3 106.00 g Na 2 CO 3
2 V0Ph  ( M HCl )  
2 mol HCl 1 mol Na 2 CO 3 (B3 – 30)
% Na 2 CO 3  100%
mass of sample (gram)
1 mol NaHCO3 84.01g NaHCO3
 V0MR - 2V0Ph  (M HCl )  
1 mol HCl 1 mol Na 2 CO3 (B3 – 31)
% NaHCO3   100%
mass of sample (gram)

For individual samples of NaOH, Na2CO3 and NaHCO3…

 V0BCG  M HCl   1 mol NaOH  40.00 g NaOH

% NaOH  1 mol HCl 1 mol NaOH  100%
(B3 – 32)
mass of sample (gram)
Note: V0-BCG = V0-Ph

 12 V0BCG  M HCl   1 mol Na 2CO3  106.00 g Na 2 CO 3

2 mol HCl 1 mol Na 2 CO 3
% NaOH  100% (B3 – 33)
mass of sample (gram)
Note: V0-Ph = ½ V0-BCG

 V0BCG  (M HCl )  1 mol NaHCO3  84.01 g NaHCO3

1 mol HCl 1 mol Na 2 CO 3 (B3 – 34)
% NaHCO3   100%
mass of sample (gram)

Free Fatty Acid (Acid Number). It is expressed as the milligram of KOH needed to neutralize
the free fatty acid released by one gram of oil due to water oxidative degradation. High value
of the acid number implies deterioration of the oil or fat. The Acid Number is computed as
follows:
 M KOH  VKOH   56.11 g KOH  1000 mg
1 mol KOH 1g (B3 – 35)
Acid Number 
mass of oil sample (gram)

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Saponification Number (Koettstorfer Number). A measure of the mean molecular weight of

the fatty acid. Expressed as the milligram of KOH required to saponify one gram of fat or oil.
In the analysis, a sample is boiled in a reflux condenser with alcoholic KOH.

 M HCl   Vblank  Vsample  HCl  1 mol KOH  56.11 g KOH  1000 mg

1 mol HCl 1 mol KOH 1(B3
g – 36)
Saponification No. 
mass of oil sample (gram)

B. Precipitation Titration

In this section, titrations involving the use of AgNO3 solutions are discussed. Argentometric
titration is used to determine chloride, bromide, cyanide and even silver. Mohr, Volhard and
Fajan Method are included in this section.

1. Solubility Product Constant

For a saturated solution of a sparingly soluble salt, equilibrium is established between the
undissolved salt and its ion in the solution. Consider a saturated solution of lead(II) chloride…

PbCl2(s)  Pb2+(aq) + 2Cl–(aq)

The mathematical expression of this equilibrium is expressed as

[Pb 2 (aq) ] [Cl - (aq) ]2

K eq 
[PbCl 2(s) ]

Since the activity of a pure substance is unity and for a solute in dilute solution is the same as
its concentration, the solubility product constant is defined as:

K sp  [Pb 2 (aq) ] [Cl  (aq) ]2

From this expression, high Ksp value means the salt is more soluble in water. If x, is the molar
solubility of PbCl2, then x moles of lead ion and 2x moles of chloride ion will be present in
solution. Therefore, the Ksp expression for PbCl2 in terms of its molar solubility is 4x3. Some
values of Ksp are given in Table B3 – 10.

Table B3 –10. Solubility product constants at 25C.

Salt Ksp Salt Ksp Salt Ksp
AgBr 5.0  10 –13
Ag2CrO4 1.2  10–12 Ca(OH)2 6.5  10–6
Hg2Br2 5.6  10–23 BaCrO4 2.1  10–5 AgI 8.3  10–17

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PbBr2 2.1  10–6 AgCN 2.2  10–16 PbI2 7.9  10–9

AgCl 1.8  10–10 Hg2(CN)2 5.0  10–40 Hg2I2 1.1  10–28
Hg2Cl2 1.2  10–18 CaF2 3.9  10–11 Ag2S 8.0  10–51
PbCl2 1.7  10–5 Mg(OH)2 7.1  10–12 PbS 3.0  10–28

2. Common Precipitimetric Methods

The equivalence point of precipitation titrations can be observed through the following:
a. Formation of a secondary colored precipitate (Mohr Method)
b. Formation of a colored complex ion (Volhard Method)
c. Formation of colored adsorption compound (Fajan Method)

Mohr Method. This method is used for the direct determination of chlorides and bromides.
The titration uses a small amount of K2CrO4 (about 1 mL of a 5% wt. K2CrO4) as indicator.
During titration, the solution must be neutral to avoid precipitation of silver oxide (pH>10) or
conversion of the indicator to dichromate (pH<6). The endpoint is observed through the
formation of a red precipitate of Ag2CrO4. The titration and indicator reactions are as follows:

Titration Reaction: Ag+ + Cl–  AgCl(s)

Indicator Reaction: Ag+ + CrO4–2  Ag2CrO4(s)

Fajan Method. The adsorption indicators are used for the direct determination of chlorides,
bromides, iodides and thiocyanates. Fluorescein, dichlorofluorescein and Eosin are used as
indicators. In the titration of chloride ion with AgNO 3, the addition of excess silver ion results
in the adsorption of this ion to the AgCl precipitate hence acquiring a positive charge and
attracts negative ion to the counter-ion layer. The indicator anion, initially yellow in color, is
then attracted to the counter-ion layer and changes color to pink, signaling the endpoint of the
titration.

Titration Reaction: Ag+ + Cl–  AgCl(s)

Indicator Reaction: AgClAg+ + DCF–  AgClAg+:DCF–

Volhard Method. This method is used for the direct determination of silver using KSCN as
titrant and ferric ions as indicator. It is also applied for the indirect determination of halides.
Titration is carried out in acidic medium to prevent precipitation of the ferric ion indicator to
its hydrated oxide form. The endpoint is observed by the formation of a red brown complex of
Fe(SCN)2+.

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Direct Titration Reaction: Ag+ + SCN–  AgSCN(s)

Indirect Titration reaction: Ag+ + Cl–  AgCl(s)
Ag+ + SCN–  AgSCN(s)

Indicator Reaction: Fe+3 + SCN–  Fe(SCN)2+

C. Complex–Formation Titration

This type of titration is usually used for the determination of cations. In this section titration
with aminocarboxylic acids and the Liebig Method for cyanides are discussed.

1. Titration with EDTA

Most metals react with Bronsted bases to form coordination compounds. Typical examples of
these Bronsted bases are water, ammonia and the halide ions. Ethylenediamminetetraacetic
acid or commonly known as EDTA is used for compleximetric titration. It is a hexadentate
ligand that is capable of bonding with metal ions. EDTA has six sites available for bonding
that include four carboxyl groups and two amino groups. Commercially, the free acid and the
dihydrate disodium salt is available. The standard solutions of EDTA combine in a 1:1 ratio
with any metal ion and titration are carried out using Eriochrome Black T (EBT) or
Calmagite. Calcium carbonate is used as primary standard dried at 110C and dissolved in
concentrated HCl solution.

a. Displacement Titration with EDTA

In the determination of cations, it is necessary to add metal cations that forms complex with
EDTA and is less stable with the analyte ion–EDTA complex. In the determination of calcium,
a small amount of magnesium ion is added using magnesium chloride in an EDTA solution. In
the first stage of the titration, calcium ion displaces the magnesium ion in the EDTA complex
and a red complex of calcium-EDTA is formed. When all calcium ions are titrated, the
magnesium ion combines with the EDTA imparting a blue color using EBT as indicator thus
signals the endpoint of the reaction.

The following reactions are observed in the titration:

Titration Reaction: Ca+2 + MgY–2  CaY–2 + Mg+2

Mg+2 + In–  MgIn–
red
Endpoint Reaction: MgIn– + H2Y–2  MgY–2 + HIn–2 + H+
red blue

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b. Back Titration with EDTA

Determination of aluminum involves back titration with EDTA. In the analysis, the solution is
buffered to pH=7 to avoid precipitation of aluminum as Al(OH)3. To ensure complete
formation of the aluminum complex, the solution is boiled and the excess EDTA is
determined by a standard magnesium solution using calmagite as indicator.

2. Determination of Cyanides and Cyanide–Halide Mixture

The dropwise addition of silver nitrate results in the formation of a soluble silver cyanide
complex:
Ag+ + CN–  Ag(CN)2–

The endpoint of the titration is observed through the formation of a faint turbid solution as
shown in the reaction:
Ag(CN)2– + Ag+  Ag[Ag(CN)2]

For a mixture of cyanide and halide, the addition of AgNO 3 causes the precipitation of CN – as
soluble Ag(CN)2– complex. Further addition of a measured excess amount of standard AgNO3
results in the formation of insoluble precipitates of Ag[Ag(CN) 2] and AgCl. The precipitate is
filtered and the excess solution is determined by a standard KSCN. This method is a
combination of Liebig and Volhard Method.

3. Determination of Nickel

A sample containing nickel was treated with ammonia solution forming a soluble
hexaamminenickel(II) complex:
Ni+2 + 6NH3  Ni(NH3)6+2
The ammoniacal solution of nickel is treated with excess standard cyanide solution. The
excess cyanide is determined using the Liebig Method.

Ni(NH3)6+3 + 4CN–1 + 6H2O  Ni(CN)4–1 + 6NH4OH

4. Determination of Mercury

In this analysis, mercury complexes with EDTA and forms a stable complex but cannot be
titrated using Calmagite or EBT indicator. Instead, a solution of MgY–2 is added in excess and
the liberated Mg+2 is titrated by EDTA. The reaction proceeds as follows:

Hg+2 + MgY–2  HgY–2 + Mg+2

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D. Oxidation – Reduction Titration

Modern methods utilize the electrical properties of materials due to their ability to accept and
donate electrons during reaction. This method of volumetric titration involves oxidation and
reduction reactions wherein reactants undergo changes in its oxidation state. Oxidation
reaction involves an increase in the oxidation number of the substance by losing electrons.
Reduction reaction, on the other hand, results in the decrease of oxidation number by gaining
electrons.

1. Permanganate Titration

In this process, potassium permanganate (KMnO4) is used as titrant and can oxidize various
ions of iron, mercury, tin and anions such as oxalate, nitrite and sulfite. It is a powerful
oxidizing agent and reduced to Mn+2 in acidic medium and to MnO2 in weakly acidic or
alkaline and neutral solutions according to the reactions:

MnO4–1(aq) + 8H+(aq) + 5e–  Mn2+(aq) + 4H2O(l)

MnO4–1(aq) + 2H2O(l) + 3e–  MnO2(s) + 4HO–(aq)

The solution of KMnO4 is quite unstable and normally kept in a colored bottle. It is a very
powerful oxidizing agent in which even water is oxidized and wavelengths of light can
actually promote such reaction. The endpoint is observed by a pink color of the solution due
to the excess addition of the titrant. Standardization of KMnO 4 is done using sodium oxalate
and arsenious oxide.

Sodium oxalate, Na2C2O4 dried at 105C is dissolved in water and sulfuric acid and titrated
with the solution, adding about 140 times the weight of dissolved primary standard. The
solution is then heated from 55-60C and titrated until a faint pink color persist after 15
minutes of stirring. The titration reaction is as follows:

5H2C2O4 + 2MnO4– + 6H+  2Mn+2 + 10CO2 + 8H2O

Arsenious oxide, As2O3 dissolved in 6N NaOH is made acidic with HCl and treated with a
dilute solution of KI that serves as a catalyst in the reaction. Titration with KMnO 4 then
proceeds until a faint pink solution is observed. The reactions are:

As2O3 + 6HO–  2AsO3–3 + 3H2O

AsO3–3 + 6H+  As+3 + 3H2O

5As+3 + 2MnO4– + 12H2O  5H3AsO4 + 2Mn+2 + 9H+

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One application of permanganate titration is the determination of iron. In the analysis, iron-
containing sample is dissolved by an appropriate solvent. However, iron was found to exist in
two oxidation states and pre-reduced before the treatment. Several metals like zinc, silver,
lead and aluminum were found to be useful for pre-reduction. A typical example is the Jones
reductor, which is composed of a vertical tube filled with amalgamated zinc. Another type is
the Walden reductor, in which metallic silver is being used. The reaction involved in the
determination of iron is

5Fe+2 + MnO4– + 8H+  5Fe+3 + Mn+2 + 4H2O

Table B3 – 11 shows other applications of permanganate titration.

Table B3 – 11. Application of Permanganate Titration.

Analyte Reaction Treatment
Metal is precipitated as oxalate
5H2C2O4 + 2MnO4– + 6H+ 
Mg, Ca, Ba, Co and titration is carried out in
2Mn+2 + 10CO2 + 8H2O
acidic medium
5HNO2 + 2MnO4– + H+  Back titration
NO2–
2Mn+2 + 5NO3– + 3H2O
5H2O2 + 2MnO4– + 6H+  Titration in acidic medium
H2O2
2Mn+2 + 5O2 + 8H2O
5Sn+2 + 2MnO4– + 16H+  Pre-reduction with Zn is
Sn
2Mn+2 + 5Sn+4 + 8H2O required
3S–2 + 8MnO4– + 4H2O  Excess alkaline KMnO4 is used
H2S
3SO4–2 + 8MnO2 + 8HO–

2. Dichromate and Ceric Titration

Dichromate and ceric ions are also used for many redox titrations due to their stability even at
higher temperatures. Potassium dichromate crystals have no water of crystallization and
usually obtained in high purity. Ceric solutions are commonly obtained from ceric ammonium
sulfate or ceric ammonium nitrate. Sodium salt of diphenylamine sulfonate and ferroin
(ferrous complex of phenanthroline) are used as indicators. The half–cell reaction for these
oxidants are:

Cr2O7–2 + 14H+ + 6e–  2Cr+3 + 7H2O

Ce+4 + e–  Ce+3

Primary standards for K2Cr2O7 and Ce+4 include pure iron, and ferrous sulfate. The half-cell
reactions are:
Fe(s)  Fe2+(aq) + 2e–
Fe2+(aq)  Fe3+(aq) + e–

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The applications of this type of titration are the same as to that of permanganate. If back
titration is to be employed in the analysis, the excess reagent is determined by a standard
ferrous solution. Such method is used in the determination of chemical oxygen demand,
which is the measure of the oxygen equivalent to the organic matter in the water sample
which can oxidized by K2Cr2O7. In the analysis of COD, the water sample is treated with
excess K2Cr2O7 and refluxed for about two hours. The excess oxidizing agent is determined
by standard FeSO4 solution with ferroin as indicator. The half-cell reactions involved are:

O2 + 4H+ + 4e–  4H2O

Cr2O7–2 + 14H+ + 6e–  2Cr+3 + 7H2O

The COD in the water sample is calculated as

1 mol K 2 Cr2 O 7 6 mol e - 1 mol O 2 32 g O 2 1000 mg

(Vblank  Vsample blank )( M FeSO4 )     
1 mol FeSO4 1 mol K 2 Cr2 O 7 4 mol e  1 mol O 2 1g
COD 
volume of sample (L)

3. Iodometric and Iodimetric Titration

Direct Titration with Iodine. Iodimetric titration involves a standard solution of iodine
solution in iodide solution forming the triiodide ion, I 3– as titrant. Freshly prepared starch
solution is used as indicator and imparts a blue color at the endpoint. The half-cell reaction for
the titrant is
I3– + 2e–  3I–

Indirect Titration with Iodine. Iodometric titration is an indirect method where the sample is
treated and iodine is released. The iodine released is titrated with a standard Na2S2O3 solution.
The reaction is governing the titration is

I2 + 2e–  2I–
2S2O3–2  S4O6–2 + 2e–

Standardization of Iodine and Na2S2O3 Solution. Iodine is standardized using sodium

thiosulfate according to the reaction:

I2 + 2S2O3–2  2I– + S4O6–2

The thiosulfate solution in turn is standardized using potassium bromate (KBrO 3), potassium
iodate (KIO3), potassium dichromate (K2Cr2O7), and metallic copper (Cu). The primary
standard reacts with excess iodine and the iodine liberated is titrated with the thiosulfate
solution The reactions are

BrO3– + 6I– + 6H+  Br– + 3I2 + 3H2O

IO3– + 5I– + 6H+  3I2 + 3H2O
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Cr2O7–2 + 6I– + 14H+  2Cr+3 + 3I2 + 7H2O

2Cu+2 + 4I–  2CuI(s) + I2

Table B3 – 12. Applications of Direct and Indirect Titration with Iodine.

Analyte Half Cell Reaction Method of Titration
+
As H3AsO3 + H2O  H3AsO4 + 2H + 2e– Direct titration
–2 –2 + –
SO2 SO3 + H2O  SO4 + 2H + 2e Back titration
+ –
N2H4 N2H4  N2(g) + 4H + 4e Direct titration
+ –
H2S H2S  S + 2H + 2e Back titration

Analytical Chemistry, B3 - 1

acid-base titration, B3 - 3
acid-base titration, applications of, B3 - 10
acids and bases, standardization of, B3 - 5, 6
acids and bases, strength of, B3 - 4
buffer solutions, B3 - 6
complex–formation titration, B3 - 16
Fajan method, B3 - 14, 15
Free Fatty Acid (Acid Number), B3 - 13
gravimetric analysis, B3 - 1

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indicators for titration, B3 - 6

methods of analysis, B3 - 1
Mohr method, B3 - 15
oxidation – reduction titration, B3 - 18
precipitation method, B3 - 2
precipitation titration, B3 - 14
Saponification Number (Koettstorfer Number)., B3 - 14
solubility product constant, B3 - 14
titration curves, B3 - 6, 9
Volhard method, B3 - 15, 16, 17
volumetric analysis, B3 - 2

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