QUANTITATIVE METHODS OF

ANALYSIS
VOLUMETRIC ANALYSIS
Titrimetric analysis
• Determining the quantity of a reagent of known concentration that is
required to react completely with the analyte. The reagent may be a
standard solution of a chemical or an electric current of known magnitude.
.

Coulometric titrations
Volumetric titrations
The quantity of charge required to
The volume of a standard reagent
complete a reaction with the analyte is
is the measured quantity.
the measured quantity
Titrimetric analysis

Any chemical reactions can be used in titrimetric methods

Condition 1: all reactions involving the titrant and analyte must be of

known stoichiometry.

Condition 2: Titration reaction must occur rapidly

Condition 3: A suitable method must be available for determining the end

point with an acceptable level of accuracy
Volumetric titration

Figure courtesy: iStock, Getty images

Volumetric titration

• A quantitative approach to determine the concentration of

the analyte.
• It involves the use of a reagent that acts as a standard
solution with a specific volume and concentration.
• The reagent is allowed to react with the analyte to calculate
its concentration.
Types of volumetric analysis
Simple titration: uses a known solution to determine the
concentration of an unknown solution

Acid-base titration

Redox titration

Precipitation titration

Complexometric titration

https://www.reagent.co.uk/blog/how-is-titration-used-in-the-pharmaceutical-industry/
Types of volumetric analysis
Back titration

• To the analyte (A) solution, an excess of

reagent B is added.
• Excess reagent is titrated against T.

•if the analyte is volatile (e.g., NH3) or an insoluble salt (e.g., Li2CO3)
•if the reaction between analyte A and titrant T is too slow for a practical direct titration
•when no suitable indication method is available for a direct titration
Types of volumetric analysis
Double
titration
• Involves two simple titrations with several components in the
titrate or unknown concentration solution.
• Two end points, two indicators (eg, phenolphthalein and methyl
orange
Fundamentals of volumetric analysis

• It must be represented in a simple equation.

• The reaction should occur rapidly.
• Satisfactory end-point requires the addition of an equivalent
amount of standard solution.
•The reaction should be simple for the detection of the endpoint.
•It doesn’t use any specialized tools.
• simple beakers like a beaker or Erlenmeyer flask, burette, and
pipette syringe are some of the essentials.
Applications of volumetric analysis

• A quantitative method widely applied for knowing the amount of

substance by examining the volume that it occupies.
• The textile industry: to determine the actual concentration of
bleaching agents used.
• Used to know the concentration of chemical substances.
• It is used in laboratories to analyse various chemical reactions.
Glossary of Volumetric titration
• A standard solution is a reagent of known concentration.
• The equivalence point is the point in a titration when the amount of
added standard reagent is equivalent to the amount of analyte.
• The end point is the point in a titration when a physical change occurs
that is associated with the condition of chemical equivalence.
• The difference in volume or mass between the equivalence point and the
end point is the titration error.
• The titration error, Et = ,Vep –Veq
where Vep is the actual volume of reagent required to reach the end
point and Veq is the theoretical volume necessary to reach end point
Glossary of Volumetric titration: Indicators
• Used to determine the end point of a titration.

Acidic soil

pH transition range required to go from one colour to another

1. When only the color of the 2. When only the color of the
nonionized form is seen, [In−]/[HIn] ionized form is seen, [In−]/[HIn] = Alkaline
= 1/10 10/1 soil

Your eyes can generally discern only one color if it is 10 times as intense as the
other
Glossary of Volumetric titration: Indicators
• pH changes from pKa-1 to pKa +1 in going from one color to another
• Corresponds to a pH change of 2 units
• Midway between the transition pH = pKa
• pKa of the indicator should be close to the pH of the equivalence
point.

A gradient of red cabbage extract pH indicator from acidic

solution on the left to basic on the right

Wikipedia
Indicators

Methyl Orange

Phenolphthalein

Alizarin red
Methyl Violet
Indicators
Indicators
Glossary of Volumetric titration
Volumetric titrations: detection of end points

• Instruments used
• Colorimeters
• Turbidimeters
• spectrophotometers,
• temperature monitors
• Refractometers
• voltmeters
• current meters
• conductivity meters
Volumetric titrations: Primary standards

• A primary standard is an ultrapure compound that serves as the

reference material for a titration or for another type of quantitative
analysis
• 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 large molar mass so that the relative error associated with
weighing the standard is minimized.
• Examples: sodium carbonate, potassium hydrogen iodate, potassium
dichromate, oxalic acid
Volumetric titrations:
Secondary standards
• A compound whose purity has been determined by chemical analysis.
• Serves as the working standard material for titrations and for many other analyses.
• Exanple: NaOH

Standard solution
• be 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.
Volumetric titrations:

Accuracy of titration can not be better than the accuracy of

concentration of the standard solution
Determination of concentration of standard solution

Direct method
• Using primary standard
Standardization
• The titrant to be standardized is titrated against primary
standard/secondary standard/measured volume of another standard
solution
Volumetric calculations:
• Millimole = 1/1000 of a mole, and the mass in grams of a millimole,
• Millimolar mass (mM) = 1/1000 of the molar mass.

Calculating the Amount of a Substance in Moles or Millimoles

Volumetric calculations:

Molar Concentration
Volumetric calculations:
Volumetric calculations:
Volumetric calculations:
Volumetric calculations:
Volumetric calculations:
Volumetric calculations:
Working with volumetric data: calculating molar concentrations from standardization data

A 50 mL of an HCl solution required 29.71 mL of 0.01963 M Ba(OH)2 to reach an end point with
bromocresol green indicator. Calculate the molar concentration of the HCl solution.
Working with volumetric data: calculating molar concentrations from standardization data
Titration of 0.2121 g of pure Na2C2O4 (134.00 g/mol) required 43.31 mL of KMnO4. What is the molar
concentration of the KMnO4 solution? The chemical reaction is
2MnO4- + 5C2O42- + 16H+ 2Mn2+ + 10CO2 + 8 H2O
 Working with volumetric data: calculating the quantity of analyte from titration data

A 0.8040 g sample of an iron ore is dissolved in acid. The iron is then reduced to Fe2+ and titrated
with 47.22 mL of 0.02242 M KMnO4 solution. Calculate the results of this analysis in terms of (a) %
Fe (55.847 g/mol) and (b) % Fe3O4 (231.54 g/mol).