Titrimetric Methods

by

Rey Y. Capangpangan, Ph.D.

Chem 20 : Analytical Chemistry (Lec
(Lec))
Chemistry Division
College of Arts and Sciences
Caraga State University

Titrimetry

Analytical methods based on determining the quantity

of a reagent of known concentration required to react
completely with the analyte
Titrations are used in analytical chemistry to
determine
Acids
Bases
Oxidants
Reductants
Metal ions
Proteins

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 Titrimetric Methods

Volumetric titrimetry
Measures the volume of a solution of known
concentration that is needed to react completely with the
analyte
Gravimetric titrimetry
The mass of the reagent is measured instead of volume
Coulometric titrimetry
The reagent is a constant direct electric current of
known magnitude the consumes the analyte; the time
required (thus, the total charge) to complete the
electrochemical reaction is measured

Terms used in Volumetric Titrimetry

Standard solution (or a standard titrant)

A reagent of exactly known concentration that is used in
titrimetric analysis
Titration
A process in which a standard reagent is added to a solution of
the analyte until the reaction between the analyte and reagent
is judged to be complete
Back-titration
A process in which the excess of a standard solution used to
consume an analyte is determined by titration with a second
standard solution
Required when the rate of reaction between the analyte and
reagent is slow or when the standard solution lacks stability

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The titration process

The titration process

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Back-titration in determining the amount of phosphate in a sample

Add measured excess of silver nitrate

(AgNO3) to a solution of the sample, which
leads to the formation of insoluble silver
phosphate

The excess AgNO3 is then back-titrated with a

standard solution of potassium thiocyanate

Terms used in Volumetric Titrimetry

Equivalence point
The point in a titration when the amount of added
standard reagent is exactly equivalent to the amount of
analyte
Endpoint
The point is a titration when a physical change occurs that
is associated with the condition of chemical equivalence
Indicators
Solutions added to the analyte solution to produce an
observable physical change (the end point) at or near the
equivalence point

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 Typical Indicator Changes

Appearance or disappearance of color

Change in color

Appearance or disappearance of turbidity

Indicator used in the precipitation titration of Ag ion with KSCN

Ferric chloride, FeCl3, reacts with thiocyanate

ions to give a red color
Indicator reaction:

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 Instruments can detect endpoints

These instruments respond to properties of the

solution that change in a characteristic way
during titration
Colorimeters
Turbidimeters
Temperature monitors
Refractometers
Voltmeters
Current meters
Conductivity meters

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Primary and Secondary Standards

Primary standard
A highly purified compound that serves as the
reference material in volumetric and mass
titrimetric methods
Secondary standard
A compound whose purity has been established
by chemical analysis and that serves as the
reference material for a titrimetric method of
analysis

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 Important requirements for a primary standard

High purity. Established methods for confirming

purity should be available
Atmospheric stability
Absence of hydrate water so that the composition of
the solid does not change with variations in humidity
Modest cost
Reasonable solubility in the titration medium
Reasonably larger molar mass so that the relative
error associated with weighing the standard is
minimized

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Desirable properties of standard solutions for a titrimetric

method

Sufficiently stable so that it is necessary to

determine its concentration only once
React rapidly with the analyte so that the time
required between additions of reagent is
minimized
React more or less completely with the analyte
so that satisfactory end points are realized
Undergo a selective reaction with the analyte
that can be described by a balanced equation

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Methods used to establish the concentration of standard
solutions

Direct method
A weighed quantity of a primary standard is
dissolved in a suitable solvent and diluted to an
exactly known volume in a volumetric flask
Standardization
The titrant to be standardized is used to titrate:
A weighed quantity of a primary standard
A weighed quantity of a secondary standard
A measured volume of a secondary solution

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Volumetric Calculations

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 Volumetric Calculations

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Calculating the molarity of standard solutions

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Calculating the molarity of standard solutions

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Calculating the molarity of standard solutions

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 Types of Volumetric Calculations

Calculating the molarities from

standardization data
Calculating the quantity of analyte from
titration data

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Computing molarities from standardization data

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Computing molarities from standardization data

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Computing molarities from standardization data

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 Computing molarities from standardization data

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Calculating the quantity of analyte from titration data

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Calculating the quantity of analyte from titration data

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Calculating the quantity of analyte from titration data

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Calculating the quantity of analyte from titration data

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Calculating the quantity of analyte from titration data

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Calculating the quantity of analyte from titration data

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Calculating the quantity of analyte from titration data

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Calculating the quantity of analyte from titration data

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Calculating the quantity of analyte from titration data

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 Typical applications of neutralization titrations

Elemental analysis

Determination of inorganic substances

Determination of organic functional groups

Determination of salts

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Elemental Analyses

Nitrogen
Proteins
Amino acids
Synthetic drugs
Fertilizers
Explosives
Potable water supplies
Soils
Dyes

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 Determination of Nitrogen

Kjeldahl method

Biuret method

Lowry method

Other methods

Dumas method

Chemiluminiscence

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Elemental analyses-based neutralization titrations

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 Determination of inorganic substances

Ammonium salts

Nitrates and nitrites

Carbonate and carbonate mixtures

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Determination of organic functional groups

Carboxylic and sulfonic acid groups

Amine groups

Ester groups

Hydroxyl groups

Carbonyl groups

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