5/6 /2 0 2 5
Volumetric Titration Methods
Volumetric titration is a quantitative analytical method used to
determine the concentration of an analyte by reacting it with a
standard solution.
By Linh Ho Thuy Nguyen
Classification diagrams for chemical analysis methods
Analytical chemistry
Qualitative Quantitative
Analysis Analysis
Chemical method Instrumental
method 1
Volumetric analysis Gravimetric analysis
Thermal analysis Electroanalytical methods Optical methods
5/6 /2 0 2 5
OBJECTIVES
Describe the principles of
volumetric analysis methods.
Differentiate between
Calculate the results after
the equivalence point
volumetric titration.
and the endpoint.
Classify various volumetric
analysis methods.
General Concept of Volumetric Analysis In the late 19th and
early 20th
The development of
Joseph Louis Gay- complexometric
Lussac in the early titrations
19th century
François Antoine redox titrations
Henri Descroizilles in
the early 19th
French chemist Jean- century
Baptiste Biot in the
early 1800s
Volumetric titration is a quantitative analytical method in which the
Titrant main purpose is to accurately measure the volume of a solution of
(Standard solution)
a given concentration required to react completely with the
analyte.
The titration is carried out by adding a standard solution of the
analyte to the analyte solution using a burette until the reaction
between the standard and the analyte is found to be complete.
Titrand The volume of the reagent is determined by the difference.
(Analyte)
Physical change
5/6 /2 0 2 5
Basic Principles of Volumetric Analysis
Reaction: A + B = C + D
Volumetric analysis is based on the
principle of equivalence, where the number The point at which the two substances A and B have completely
of moles of the substances involved in the reacted with each other is called the equivalence point (EP).
reaction must be equivalent when the
reaction reaches completion. Ex. In the titration of sodium chloride with silver nitrate, the equivalence
The direct or indirect changes in the point is reached after adding exactly one mole of silver ions for each
concentration of the ions of the substance mole of chloride ions present in the sample.
under study in the solution
NaCl + AgNO3 AgCl + NaNO3
1 mol 1 mol
In practice, it is not possible to determine the exact equivalence point,
but only the point at which the titration process should be stopped (the
endpoint of the titration process).
The endpoint of the titration can be determined by specific observable
signs, such as a change in the color of a substance called an indicator,
the appearance of a precipitate, etc.
Equivalence Point and Endpoint
Equivalence Point Endpoint Titration Error
The equivalence point in titration The endpoint is the point at which The difference between the
is the theoretical point where the a physical change occurs, such as equivalence point and the
amount of titrant added is a color change of an indicator, endpoint is known as titration
chemically equivalent to the signaling the completion of the error. It is calculated as the
amount of analyte in the sample. reaction. It is often slightly difference between the theoretical
This point is determined by the different from the equivalence volume needed to reach the 3
stoichiometry of the reaction. point due to titration error. equivalence point and the actual
volume used to detect the
endpoint.
E =V –V
t eq fin
Veq: Theoretical volume of the reagent needed to reach the equivalence point.
Vfin: The actual volume used to detect the endpoint of the reaction
The closer the endpoint of the titration process is to the equivalence point, the
more accurate the analysis results will be.
5/6 /2 0 2 5
Requirements of Volumetric Analysis
•The reaction must occur quickly (high reaction rate) and completely
(large equilibrium constant).
•The reaction must proceed according to the exact stoichiometric
coefficients (stoichiometrically valid), with stable reaction products.
•The reaction must be selective.
•The reaction must be quantitative (with an appropriate indicator to
determine the equivalence point).
Methods to Determine the
Equivalence Point
Chemical Indicators
Chemical indicators are substances added to the solution
during titration that change color in response to changes in
pH, redox potential, or other relevant factors.
Internal Indicators
Internal indicators are added directly to the solution being
titrated. They include color indicators (methyl orange, 4
phenolphthalein), precipitation indicators (potassium
chromate), and fluorescent indicators (fluorescein).
External Indicators
External indicators are kept outside the solution and are
used with tools like glass rods to take a sample of the
solution and react it with a reagent, as in the case of starch-
impregnated paper.
Physicochemical Indicators
Physicochemical indicators measure the color change of the
solution using spectrophotometric methods or
electrochemical methods like potentiometry, conductometry,
or amperometry.
5/6 /2 0 2 5
Standard Solutions
1 Definition
A standard solution is a reagent with a known
concentration used for titration in volumetric analysis
methods. It is crucial for accurate and precise results.
2 Requirements
An ideal standard solution should be stable, react quickly
with the analyte, and lead to a complete reaction to
5
accurately reach the endpoint.
3 Methods to Determine Concentration
The concentration of a standard solution can be
determined by direct methods, where a known weight of
primary standard is dissolved and diluted, or by
comparison with a standard sample (calibration).
4 Expression of Concentration
The concentration of a standard solution is typically
expressed as molarity (moles per liter) or normality (gram
equivalents per liter).
5/6 /2 0 2 5
Primary Standards
1 High Purity
Primary standards are compounds of very high purity (typically
99.95%) used as references in volumetric and gravimetric
methods. Their purity is crucial for accurate analysis.
2 Stability in Air
Primary standards should be stable in air, meaning they should
not react with atmospheric components like oxygen or moisture,
which could alter their composition.
3 No Hydration Water
Primary standards should not contain hydration water, as this
can change their composition depending on the relative
humidity. This ensures consistent and predictable results.
4 Good Solubility
Primary standards should be readily soluble in the medium used
for titration, allowing for complete reaction and accurate
determination of the equivalence point.
Secondary Standards
Purity Determination
Secondary standards are compounds whose purity must be
determined by chemical analysis. They are used to calibrate
standard solutions or to verify the accuracy of analytical
methods. 6
Examples
Examples of secondary standards include sodium tetraborate
decahydrate (Na₂B₄O₇·10 H₂O) and oxalic acid dihydrate
(C₂H₂O₄·2 H₂O). These compounds require specific drying
procedures before use.
5/6 /2 0 2 5
Types of Chemical Indicators
Type Description Examples
Single Substance Indicators Methyl red
consisting of a
single compound. Methyl red
Two Substances Indicators Tashiro's reagent
composed of two (methyl red and
substances that methylene blue)
interact to produce
a color change.
Indicators
Multiple Substances Universal indicator
containing multiple
substances that
create a range of
color changes over
a wide pH range.
Importance of Volumetric Analysis
Accurate Analysis
Volumetric analysis is a highly accurate method for determining the
concentration of substances, making it essential in various fields,
including chemistry, pharmaceuticals, and environmental monitoring.
Precise Measurements
The method relies on precise measurements of volumes and the
stoichiometry of chemical reactions, ensuring reliable and reproducible 7
results.
Cost-Effective Technique
Volumetric analysis is often a cost-effective technique compared to
other analytical methods, making it suitable for routine analysis and
quality control.
Versatile Application
Volumetric analysis is applicable to a wide range of substances and
reactions, making it a versatile tool for various analytical needs.
5/6 /2 0 2 5
Common Volumetric Analysis Methods
1 Acid-Base Titration (Neutralization Methods)
1
Based on the neutralization reaction between an acid and a base.
2 Redox Titration
Based on the electron transfer reaction between an oxidizing
agent and a reducing agent.
3 Complexometric Titration
Based on the complex formation reaction between a metal ion
and a complexing agent.
4 Precipitation Titration
Based on the formation of a precipitate when two reacting
substances combine.
Acid-Base Titration
Acid-base titration is used to determine the concentration of an acid
or base in a solution.
An example is using a standard NaOH solution to determine the
concentration of HCl.
NaOH + HCl NaCl + H 2O
Na2CO3 + 2HCl 2NaCl + CO2 + H2O 8
Indicators like phenolphthalein or methyl orange are often used to
signal the endpoint of the titration.
• A strong acid react with a strong base to form a neutral (PH=7) solution.
• A strong acid react with a weak base to form an acidic (PH<7) solution.
• A weak acid react with a strong base to form an a basic (PH>7) solution.
5/6 /2 0 2 5
Redox Titration
Redox titration is used to determine the concentration of an
oxidizing or reducing substance in a solution.
An example is using a standard KMnO₄ solution to determine the
concentration of Fe²⁺.
5Fe2+ + Mn7+ + 8H+ 5Fe3+ + Mn2+ + 4H2O
Complexometric Titration
Complexometric titration is used to determine the concentration of
9
metal ions in a solution.
An example is using a standard EDTA solution to determine the
concentration of Ca²⁺.
Hg2+ + 4I- HgI42-
5/6 /2 0 2 5
Precipitation Titration
Precipitation titration is used to determine the concentration of an
ion or compound in a solution through a precipitation reaction.
An example is using a standard AgNO₃ solution to determine the
concentration of Cl⁻.
AgNO3 + NaCl AgCl + NaNO3
Direct titration
Gradually add the standard solution from the burette into the titration solution contained in the conical
flask. Based on the consumed volume of the standard solution, the concentration of the analyte can be
calculated
Calculate based on molarity Calculate the equivalent concentration of the
Na2S2O3 solution.
Q1: Calculate the molarity of a NaOH solution,
10
knowing that when titrating 20.0 mL of this solution, Q4: It is known that when an excess of pure KI
it required exactly 22.75 mL of 0.1060 M HCl solution is added to 20.0 mL of 0.05N K2Cr2O7
solution. solution containing H2SO4 as the medium, the
Q2: When titrating 0.2275 g of pure Na2CO3 until released I2 is titrated with exactly 19.8 mL of the
CO2 is released, it required exactly 22.35 mL of HCl Na2S2O3 solution.
solution. Calculate the molarity of that HCl solution.
Q3. A solution containing 50.0 mL of 0.150 M acetic
acid is titrated with 0.200 M NaOH. Calculate the
volume of NaOH needed to reach the equivalence
point.
5/6 /2 0 2 5
Indirect Method
This titration method is used to quantify substance X when direct titration with a specific reagent
cannot be performed. The analyte X is converted into a suitable compound containing at least one
element that can be directly determined by an appropriate reagent."
Reaction with Excess Reagent Applications
The analyte reacts with a known excess of a reagent. Indirect titration is used for analytes that don't react
This excess reagent is then titrated with a standard directly with the titrant or when the analyte is unstable.
solution.
1 2 3
Back Titration
Ba2+
To quantify Ba²⁺, an excess of complexon III is
The excess EDTA (accurate quantity)
added, and the excess complexon is titrated using
standard MgCl₂. Quantify the excess using standard MgCl2
Q5. To quantify chromium (Cr) in steel, a 1.0750 g steel sample is decomposed into a solution, and Cr³⁺ is
completely oxidized to CrO₄²⁻. Then, 25.0 mL of 0.0410 M FeSO₄ solution and a sufficient amount of dilute
H₂SO₄ are added as the medium. The excess Fe(II) is titrated with 3.70 mL of 0.0400 M KMnO₄ solution.
Calculate the chromium content in the steel
Indirect Method
Reaction with Excess Reagent Applications
The analyte reacts with a known excess of a reagent. Indirect titration is used for analytes that don't react
This excess reagent is then titrated with a standard directly with the titrant or when the analyte is unstable.
solution.
1 2 3
Back Titration
The excess reagent is titrated with a standard solution, 11
allowing the calculation of the original analyte
concentration.
Stoichiometric Calculation Analyte Concentration Calculation Error Considerations
The amount of excess The original concentration of the Indirect titration can be more
reagent is calculated from analyte is then calculated by prone to errors due to the
the volume of titrant used in subtracting the amount of excess additional steps involved. Careful
the back titration, using the reagent from the initial amount execution and accurate
known concentration of the added and using the stoichiometry measurements are crucial.
titrant and the stoichiometry of the reaction between the analyte
of the reactions involved. and the reagent.
5/6 /2 0 2 5
Advantages and
Disadvantages of Direct and
Indirect Methods
Method Advantages Disadvantages
Direct Simple and Not suitable for all
straightforward analytes
Indirect Applicable to a More steps,
wider range of increased
analytes potential for errors
Instruments used in volumetric titration
1.Burette: A graduated glass tube used
to deliver precise volumes of titrant.
2.Pipette: A tool for accurately
measuring and transferring a specific
volume of liquid.
3.Conical Flask (Erlenmeyer Flask): Used
to mix the analyte solution with the
titrant. 12
4.Volumetric Flask: For preparing
standard solutions at a specific volume.
5.Indicator: A chemical that changes
color at the endpoint of the titration.
6.Funnel: For transferring liquids into the
burette or flask without spills.
7.White Tile: Often placed under the
flask to better observe color changes
during titration.
5/6 /2 0 2 5
The tolerances of some instruments used in titration
1.Burette:
1. Tolerance: ±0.01 mL to ±0.02 mL
2. Errors can arise from incorrect readings of the meniscus or parallax error.
2.Pipette:
1. Tolerance: ±0.01 mL to ±0.02 mL for volumetric pipettes; ±0.1 mL for graduated pipettes.
2. Errors can occur due to improper technique, such as not allowing the liquid to drain completely.
3.Conical Flask (Erlenmeyer Flask):
1. Tolerance: Generally not specified for volume, but significant deviations can affect the reaction mixture.
2. Errors can stem from miscalculating the initial volume or losing liquid during transfer.
4.Volumetric Flask:
1. Tolerance: ±0.1 mL for a 1 L flask; smaller flasks may have tighter tolerances.
2. Errors can occur if the liquid level is not exactly at the calibration mark.
5.Graduated Cylinder:
1. Tolerance: ±0.1 mL for small cylinders (e.g., 50 mL) and ±1 mL for larger cylinders (e.g., 1 L).
2. Errors may arise from improper meniscus reading.
6.Digital Balance:
1. Tolerance: ±0.001 g to ±0.01 g, depending on the precision of the balance.
2. Errors can occur from environmental factors, like vibrations or air currents.
Factors Affecting Titration Accuracy
Temperature Indicator Choice
Temperature fluctuations can affect the volume of The indicator used should have an
solutions and reaction rates, impacting the appropriate color change range
accuracy of the titration. that is close to the equivalence
point of the titration. The
indicator's concentration and the
sharpness of its color change can
impact the endpoint 13
determination.
Flask Size and Shape Droplet Formation
The size and shape of the flask used can affect The formation of droplets during
the accuracy of the titration. A larger flask might titration can introduce errors.
be needed for more accurate measurements. Using a burette with a fine tip and
a standardized procedure can help
minimize droplet formation.
5/6 /2 0 2 5
Applications of Titration Techniques
Food Chemistry
Titration is used to determine the acidity of foods like
vinegar and fruit juices.
Environmental Analysis
Titration is used to determine the concentration of
pollutants like heavy metals in water samples.
Pharmaceutical Industry
Titration is used to control the quality of drugs and other
pharmaceutical products.
Industrial Processes
Titration is used to monitor the concentration of reactants
and products in industrial processes.
VOLUMETRIC (Titration) CALCULATIONS
14
