Chapter II: Titrimetric Method of Analysis

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Outline
 Overview

 Terminology and Definitions

 Basic Concept

 Endpoint detection

 Reaction Types

 Titration Types and Calculation

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 Titrimetric Method: Introduction
 Volumetric analysis: analytical methods whereby the exact
volume of a solution of known concentration actually consumed
during the course of an analysis is considered as a measure of the
amount of active constituent in a given sample.
 An analyte is chemically reacted with a standard solution of reagent of
known concentration or with that which can be precisely determined.
 To the analyte solution, increments of a standardized solution of a
reagent are added gradually until the entire amount of analyte has
reacted.

 The concentration and exact volume of titrant added are used to calculate the
purity (amount) of analyte

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 Titrimetric Method: Introduction

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 Titrimetric Method: Introduction
The volume of reagent needed to complete the titration is determined from
the difference between the initial and final readings of burette.

Schematic view of the burette used for titration

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 Terms used in the Titrimetry:
 Titrant: a solution of the known concentration of the standard
substance, which is added to the sample solution from the burette.
 Titrand: this is a solution of the unknown sample whose
concentration is to be determined.
 Titration is the process of adding and then actually measuring the
volume of titrant consumed in the assay. This volume is usually
measured by the help of a calibrated burette.
 Equivalence point: this is a point where the reaction between the
titrant and titrand are completed and it can be detected by the
colour change of the indicator.
 The equivalence point is the ideal (theoretical) result we seek in a titration.
 What we actually measure is the end point, which is marked by a sudden
change in a physical property of the solution.

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 Endpoint of a titration
 The endpoint of a titration may be determined using an
indicator, which is added to the analyte solution.
 The indicator has a property that changes abruptly near the endpoint.
 E.g. a substance that have distinctly different colours in acidic and
basic media,
 The change is caused by the appearance of excess titrant or
disappearance of analyte.
 In an ideal titration, the visible end point coincides
with the equivalence point; but in practice usually some small
difference occurs.
 As a result, we get a titration error, the difference between the end
point and the equivalence point, which leads to overtitration.

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 Endpoint of a titration
 Potentiometric titration is an alternative to color indicators for
endpoint detection. allows for automation and sometimes provides
more sensitive endpoint detection.
 Potentiometry: This is mainly used in the determination of potential of
sample solution when the electrodes are immersed in the solution.
 A two-electrodes system is placed in the titration solution, associated
with a voltmeter.
 One electrode acts as an indicator electrode, and the potential of the
indicator electrode changes as a function of changes in analyte
concentration.
 The other electrode is called the reference electrode, and the potential
of this does not change during titration.
 The voltmeter measures the difference between the potential of the
indicator electrode and the reference electrode, and this potential is
plotted as a function of the added amount of titrant.
 The resulting titration curve is used to determine the endpoint of
titration .
 Other methods: Color change without indicator, Formation of precipitate ,
Spectroscopy, etc
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 Endpoint of a titration

 Factors affecting end point detection

 Indicator selection
 Color change detection
 Quantity of indicators: generally, indicators are added in a
very small quantity approximately 0.0001-0.0004% of the solution
being titrated (to make the colour change visible )
 Presence of colloidal substances: Colloidal particles are
having property to adsorb ions on their surface and this property
leads to the problems in detection of end point.
 Possibility of either premature or delayed indicator color change and hence, the
errors in detection of endpoint.

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 Requirements for titration
 A number of requirements should be fulfilled for a successful titration;

 The titration reaction must be well defined without side reactions.

 The reaction must be essentially complete (approximately 100% of

analyte must be converted to product).

 Other substances in the sample must not react with the reagent.

 The reaction rate should be high (reduces the analysis time ).

 The equivalence point should be clearly detected (A convenient

method of endpoint detection must be available ).

 The exact concentration of reagent must be known

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 Titrimetry…
Advantages:
• Capable of higher degree of precision and accuracy
• Analysis can be automated
• Cheap to perform and do not require specialized apparatus
• Absolute methods
Limitations:
• Insensitive
• Time consuming if not automated
• Require large amount of sample and reagent

• Reactions should be rapid and complete

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 Titrimetric
 To achieve high accuracy in titration, it is essential to know the exact
concentration of titrant
 In many cases the titrant is not available in a stable form of well-defined
composition.
 If this is true, the titrant must be standardized (usually by volumetric
analysis) against a compound that is available in a stable, highly pure form
(i.e., a primary standard).
 A primary standard is a chemical reagent with the following
characteristics:
 Has a high chemical purity (>99.95%);
 Has a well defined chemical composition
 Does not change the composition during storage.
 Should be a strong electrolyte & Must have good solubility in the titration
solvent
 It must be non-toxic & Should be involatile;
 It should have a high relative molecular weight so that weighing errors may be
negligible.

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 Primary standard
 The most commonly used primary standards are:;
 Acid- base reactions: sodium carbonate Na2CO3, sodium tetraborate
Na2B4O7, potassium hydrogenphthalate KH(C8H4O4),
potassium hydrogeniodate KH(IO3)2.
 Complex formation reactions: pure metals ( zinc, copper, magnesium
and manganese) and salts, depending upon the reaction used.
 Precipitation reactions: silver, silver nitrate, sodium chloride, potassium
chloride and potassium bromide.
 Oxidation- reduction reaction: potassium dichromate (K2Cr2O7), potassium
bromate (KBr), potassium iodate ( KIO3), sodium oxalate Na2C2O4 and pure iron.

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 Primary standard
 Titrant solutions of primary standards can be made directly
by accurate weighing of the standards and subsequent
dissolution and dilution to a specific volume.
 Such solutions will have an accurately known concentration.
 In some cases, such solutions are used directly to titrate the
analyte.
 In other cases, however, it is not possible to obtain a
primary standard that are suitable for direct titration.
 In this case the solution of titrant is first standardized with a solution
of a primary standard to determine the exact concentration of the
titrant.

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 Secondary Standard Solution
 The many reagents used as titrants, such as HCl and NaOH, are not
available as primary standards
 we prepare titrant with approximately the desired concentration, and
determine the concentration of titrant.
 Once its concentration has been standardized with primary standard
solution, it is then used as secondary standard solution. Example; NaOH
vs KHP.
 Standardization: the process by which the concentration of a solution is
determined.
 Standard Solution: A solution of accurately known concentration.
 The secondary standard solutions must have the following features:
 Its concentration should be stable for longer period of time.
 It should have the ability to rapidly react with analyte to complete the reaction
by simple chemical equation.
 It should have the ability to produce the sharp end point.

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 Titrimetry…
 Standard solutions are prepared in two ways:
 Direct Method: a primary standard compound is carefully weighed and
dissolved in exactly known volume of solution.
 Indirect Method: a solution is prepared to give approximately the
desired concentration, and this is standardized by titrating against a
weighed quantity of a primary standard. Example; NaOH vs KHP.

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 Main steps in a Titration
 Sampling

 Titrant preparation

 Selection of end point detection method

 Titrant standardization

 Sample preparation and conversion to a measurable form

 Sample titration with the titrant solution

 Data analysis and reporting

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 The basic requirements or components of a volumetric method are:
 A standard solution (i.e., titrant) of known concentration which reacts
with the analyte in a known and repeatable stoichiometry (i.e.,
acid/base, precipitation, redox, complexation).
 A device to measure the mass or volume of sample (e.g., pipet,
graduated cylinder, volumetric flask, analytical balance).
 A device to measure the volume of the titrant added (i.e., buret).
 If the titrant-analyte reaction is not sufficiently specific, a pretreatment to
remove interferents.
 A means by which the endpoint can be determined. This may be an
internal indicator (e.g., phenolphthalein) or an external indicator (e.g.,
pH meter).

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 The most common apparatus used in volumetric determinations are
the pipette, burret, measuring cylinder, volumetric and conical
(titration) flask.
 Reliable measurements of volume is often done with the help of a
pipet, burret, and a volumetric flask.
 The conical flask is preferred for titration because it minimizes the
loss of the titrant during titration.


 Volumetric Apparatus (Reading Assignment):

 Volumetric flasks, Graduated cylinders, Burettes, Pipettes,
 Other fundamental apparatus in Pharmaceutical Analysis: Apparatus
for filtration, Balances

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 Direct titration Vs Back titration
• Direct titration is a type of titration where the titrant is
allowed directly to react with the analyte.

 E.g. analysis of Cl- in raw materials using Ag+ as titrant

• Back titration is a type of titration where a measured

amount of a reagent is added to the analyte so that there is a
slight excess. After the reaction is allowed to go
completion, the amount of excess (un-reacted) reagent is
determined by titration with another standard solution.

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 Back titration:When?
 the reaction is slow to go to completion

 the sample is volatile (e.g. NH3)

 Substance, which require heating with standard reagent

 the sample is insoluble (e.g. ZnO)

 the end point of the back titration is clearer than the end
point of the direct titration.

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 Examples

• Aspirin analysis
• Analysis of formaldehyde, H2CO.

– H2CO + I3 (excess) + 3OH- (aq) HCO-2 + 3I- (aq) + 2H2O

(aq)

– Unreacted I3- (aq) + 2 S2O32–(aq) S4O62- + 3I- (aq)

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 Back titration with Blank determination
 Blank titration is a titration with out the analyte.
 Back titrations are often combined with blank titrations, particularly if there
is some loss of reagent during the assay (e.g. as a result of splashing or
vigorous boiling) or the concentration of a volumetric reagent changes
during the assay
 If the procedure involves heating and subsequent cooling of the
sample (e.g. to allow sample to dissolve), some of the volumetric reagents
may be lost either by evaporation or mechanically due to splashing or
bubbling. The indicator might also react with the reagent
 Blank titration is used to determine the exact amount of
the reagent, added in excess, which would react with analyte.
 The blank determination must be identical to the rest of the test

determining in every way except that there is no sample in the blank. This

means that heating times, dilution etc, must be duplicated exactly.

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 Classification of volumetric methods:


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Calculations in titrimetry.

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 Calculations in titrimetry
Preparation of a solution a pure, solid chemical:
• Vdesired X Ndesired X equivalent weight of solute = grams to be weighed
or
• Vdesired X Mdesired X molecular weight of solute = grams to be weighed
Preparation of solution by dilution
Or

Standardization with a primary standard

•VT x NT = grams (primary standard)/Equivalent weight (primary standard)
•VT x MT = grams (primary standard)/Molecular weight (primary standard)
Standardization with another standard solution:
•VT x NT = VST x NST or VT x MT = VST x MST

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 Volumetric Calculations Using Normality and Equivalent Weight

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 Calculation examples


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 Calculation examples
5. A 0.1 M solution of hydrochloric acid is standardized to determine the
exact concentration of HCl. Na2CO3 is used as the primary standard. An
amount of 0.1006 g of Na2CO3 (mm=105.99 g/mol) is dissolved in water and
diluted to 20 mL. This solution is titrated with 0.1 M HCl, and the
consumption of 0.1 M HCl is 18.55 mL. The following reaction occurs:
𝟐𝑯𝑪𝒍 + 𝑪𝑶𝟑𝟐− 𝟐𝑪𝒍− + 𝑯𝟐𝑪𝑶𝟑

6. Titration of 0.2121 g of pure NaC2O4 (134 g/mol) required 43.31 ml of

KMnO4. what is the molarity of the KMnO4 solution? The chemical reaction
is. (Ans. 0.01462M)
2 MnO-4 + 5C2O2-4 + 16H+ 2Mn2+ + 10CO2+2 +8H2O

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 Titration of a pharmaceutical ingredient and calculation of purity (assay)

#7: To establish the purity of the API ketoprofen (anti-inflammatory drug),

0.1996 g is weighed on an analytical balance and dissolved in 25 mL of
ethanol 96% (v/v); 25 mL of water is added to the solution. The solution is
titrated with 7.85 mL of 0.1006 M NaOH to the equivalence point. Calculate
the percentage purity of Ketoprofen.

#8: A pharmacist wants to determine the percentage of drug using a

titration. He dissolved 0.5 gm of the drug in 30 ml of 0.1 M NaOH and He
titrated the excess NaOH with 0.1 M HCl. 3 ml of HCl was consumed in
the titration. Assuming 1:1 reaction, calculate the percentage of drug in
the sample taken (M.wt of is 180 gm/mol).

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 The Titration process


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 The Titration process
 Region 3 –At equivalence point:
 the reagent added is the amount that is chemically equivalent
to the amount of substance being determined (analyte).
 the point at which there would be neither T nor A present if the
reaction went to completion.
 only Px and Py would be present in measurable amounts
 Region 4 –After equivalence point:
 the amount of reagent added is higher than the amount of substance
being determined.
 A becomes the limiting reagent and therefore there will be very little A,
and therefore there will be very little A(if any, depending on whether
the reaction went totally to completion, in which case [A] = 0) in
solution.
 Only T, Px, and Py are present in measurable amounts in the titration
flask .
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 Titration curves
• Titration curve is plot of a variable related to a
relevant concentration as y-axis versus some measure of
the amount of titrant (e.g. volume) on the X-axis.
• A titration curve provides us with a visual picture of how a
property of the titration reaction changes as we add
the titrant to the titrand.
• Titration curve define the properties required of an indicator
and allow us estimate the error associated with the titration
methods.

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End point detection from a titration curve

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 Titer Value


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Thank you!

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