CC 102: QUALITATIVE AND QUANTITATIVE CHEMISTRY

College of Liberal Arts, Sciences and Education

Prepared by: ERWIN R. ABRENCILLO, PhD
DENNIS M. DIMARANAN

MODULE 9
VOLUMETRIC ANALYSIS

Brief Introduction or Description

This module discusses volumetric analysis, one of the quantitative analysis in analytical
chemistry which involves the determination of volume of an analyte. This includes the factors of
solubility, titration principles and titration calculations.
Learning Outcomes:
By the end of the module, you should be able to:
1. Explain the factors affecting the solubility of a solute in each solvent and its rate of solution.
2. Determine the principle governing titration.
3. Perform titration calculations.

Lesson 1 Factors of Solubility

The solubility of a solute is: the maximum amount of solute that can dissolve in a certain
amount of solvent or solution at a certain temperature.
MAIN FACTORS THAT AFFECT SOLUBILITY:
Nature of the solute and solvent – The amount of solute that dissolves depends on
what type of solute it is. While only 1 gram of lead (II) chloride can be dissolved in
100 grams of water at room temperature, 200 grams of zinc chloride can be dissolved.
This means that a greater amount of zinc chloride can be dissolved in the same
amount of water than lead II chloride.
Temperature -- Generally, an increase in the temperature of the solution increases
the solubility of a solid solute. For example, a greater amount of sugar will dissolve
in warm water than in cold water. A few solid solutes, however, are less soluble in
warmer solutions. For all gases, solubility decreases as the temperature of the
solution rises. An example of this is Soda. The solubility of the carbon dioxide gas
decreases when a soda is warm, making the soda flat.
Pressure -- For solid and liquid solutes, changes in pressure have practically no effect
on solubility. For gaseous solutes, an increase in pressure increases solubility and a
decrease in pressure decreases solubility. Example: When the cap on a bottle of
soda pop is removed, pressure is released, and the gaseous solute bubbles out of
solution. This escape of a gas from solution is called effervescence.
FACTORS THAT AFFECT THE RATE OF SOLUTION:
The rate of solution is: a measure of how fast a substance dissolves.
Size of the particles -- When a solute dissolves, the action takes place only at the
surface of each particle. When the total surface area of the solute particles is increased,
the solute dissolves more rapidly. Breaking a solute into smaller pieces increases its
surface area and increases its rate of solution.
Stirring -- With liquid and solid solutes, stirring brings fresh portions of the solvent in
contact with the solute. Stirring, therefore, allows the solute to dissolve faster.

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 CC 102: QUALITATIVE AND QUANTITATIVE CHEMISTRY
College of Liberal Arts, Sciences and Education
Prepared by: ERWIN R. ABRENCILLO, PhD
DENNIS M. DIMARANAN

Amount of solute already dissolved – When you have very little solute in the solution,
dissolving takes place quickly. When you have a lot of solute in the solution, dissolving
takes place more slowly.
temperature -- For liquids and solid solutes, increasing the temperature not only
increases the amount of solute that will dissolve but also increases the rate at which
the solute will dissolve. For gases, the reverse is true. An increase in temperature
decreases both solubility and rate of solution.
Lesson 2 Volumetric Analysis or Titration

The quantity of an analyte in a sample can be expressed in terms of mass, volume, concentration,
moles, or relative abundance.

Volumetric analysis is a quantitative analytical method that measures the volume of the analyte directly
or the concentration or volume of the analyte indirectly by measuring the volume of a second substance,
called the titrant, that reacts with the analyte in a known proportion. The second method is called
titrimetric or titration analysis.

Volumetric analysis is a quantitative analytical method that measures the volume of the analyte
or the volume of a second substance that reacts with the analyte in a known proportion.

Titrimetric (titration) analysis is a quantitative analytical method used to determine the

concentration of an analyte using a known concentration of a second solution.

Examples of titrimetric analysis (titrations) used in industry are

• determining concentrations of components in wastewater analysis,

• determining contamination levels in river waters and acid rain,
• determining levels of acids in juices and other foodstuff in nutrition,
• determining drug concentrations in medicine.

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 CC 102: QUALITATIVE AND QUANTITATIVE CHEMISTRY
College of Liberal Arts, Sciences and Education
Prepared by: ERWIN R. ABRENCILLO, PhD
DENNIS M. DIMARANAN

The diagram above shows that there are three broad categories of titration, based on the type of
reaction that occurs between the analyte and the titrant. These are neutralization reactions, redox
(oxidation–reduction) reactions, and precipitation reactions.

The type of titration is chosen depending on the nature of the analyte. Neutralization titrations can be
used to quantify acids or bases, while substances that undergo redox reactions can be quantified by
performing redox titrations, and substances that form sparingly soluble salts can be measured using
precipitation titrations.

Titration is a quantitative analysis to determine the concentration of an unknown solution by adding a

solution of known concentration in a drop at a time. By this process, the acid or base of a known
concentration completely neutralizes the acid or base of the unknown concentration. The actual
reaction that takes place during neutralization is between a hydrogen ion from acid and hydroxide ion
from base that combine to form water. It is important to maintain a uniform pH throughout the process.
Hence analyte and titrate should be of equal concentration. Involving strong titrate and a diluted analyte
or vice versa will affect the physical of the analyte. The process is generally monitored by pH electrodes
or indicators.

The solution of known concentration is the titrate and the solution whose concentration is to be
determined is the analyte. The equivalence point of this process is obtained when the titrate completely
neutralizes the base or acid in the analyte.

Titration process

The analyte is measured and filled in a beaker. A few drops of an acid base indicator, such as methyl
orange or phenolphthalein, is added to the analyte.

Phenolphthalein remains colorless in acid, but turns pink in the presence of a base. Similarly, methyl
orange is a reddish-orange powder that turns to deep red in an acid and pales out to yellow in a base.

A standard solution is taken in a burette to start the process. The standard solution is allowed to drip
slowly into the beaker containing the analyte. The process is carried out until the color of the analyte
changes, indicating the arrival of an end point. This means that all of the base or acid in the analyte
has been completely neutralized by the titrate.

The volume change of the standard solution at which the end point occurs is noted. This volume
indicates the amount of titrate that has been used to neutralize the analyte. These values are then
used in further calculations.

Types of Titration

• Acid-base titrations: Acid-base titration mainly depends on the neutralization between acid
and base when mixed in solution. More significantly, the strength of an acid is determined
using a standard solution of a base. This process is also called acidimetry.

• Redox titrations: These kinds of titrations are almost similar to the volumetric acid. Base
titrations except that here, the reactions involved are Redox reactions.

• Precipitation titrations: Precipitation titration is based on insoluble precipitation where two

reacting substances are brought in contact, which is called precipitation titration. The titrant
reacts with the analyte and forms an insoluble material. The titration continues until the
analysis is completely over. When the titrant is high it reacts with the indicator and signals to
end the titration process.
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 CC 102: QUALITATIVE AND QUANTITATIVE CHEMISTRY
College of Liberal Arts, Sciences and Education
Prepared by: ERWIN R. ABRENCILLO, PhD
DENNIS M. DIMARANAN

• Complexometric titrations: The complexometric titration is where an undivided complex is

formed at an equivalence point. This is greater than the precipitation titrations, and there will
be no error due to co-precipitation.

Lesson 3 Application of Concepts of Volumetric Analysis

The diagram below shows the setup of a typical neutralization titration. Let us assume that the analyte
is an acid and the titrant is a base.

An accurately known volume of the acid, whose concentration is unknown, is pipetted into a conical
flask. The basic titrant solution has a concentration that is known exactly, and therefore, this solution is
referred to as a standard solution. The titrant is added slowly to the analyte from the buret until the
indicator changes color, at the end point, indicating that the reaction is complete and the neutralization
of all the analyte in the conical flask has occurred.

The volume of the titrant added (the titer) is recorded. This process is repeated several times in different
runs to ensure precision.

It is important to remember that the burette readings are taken at eye level to avoid parallax error.

Let us investigate how to calculate the concentration of an acid from the results of a titration experiment.

The three variables commonly used in titration calculations are

• 𝑛, the number of moles (unit mol),

• 𝑉, the volume of the solution (unit typically expressed as mL, L, or dm3),
• 𝑐, the concentration of the solution (typically expressed as molarity: mol/L or mol/dm3).

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 CC 102: QUALITATIVE AND QUANTITATIVE CHEMISTRY
College of Liberal Arts, Sciences and Education
Prepared by: ERWIN R. ABRENCILLO, PhD
DENNIS M. DIMARANAN

The relationship between these three quantities is

𝑛=𝑐𝑉.

The tables below show the data that is collected during a neutralization titration between an acid as an
analyte, HCl, and a standard base as a titrant, NaOH.

It is important to ensure that the acid–base reaction equation is balanced before doing calculations,
since the stoichiometric ratio of the reactants influences the calculations. The schematic below shows
the balanced reaction equation, the molar ratio of the reaction substances (from the stoichiometric
coefficients), and the three steps for determining the concentration of the analyte:

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 CC 102: QUALITATIVE AND QUANTITATIVE CHEMISTRY
College of Liberal Arts, Sciences and Education
Prepared by: ERWIN R. ABRENCILLO, PhD
DENNIS M. DIMARANAN

In the first step, the number of moles of the titrant is calculated. Before doing this, however, the average
titer must be calculated from the titer values of the three runs and the volume unit converted
from milliliters to liters since the concentration of the solution is expressed in molarity, whose unit
is mol/L. Remember that sometimes, molarity is expressed as mol/dm3, which is equivalent to the
unit mol/L since 1 dm3 = 1 L.

The average volume of titrant is calculated by adding the volume of titrant delivered from the burette
from each run and dividing by the number of runs:

average volume of titrant =(14.50 mL + 14.48 mL + 14.47mL) ÷ 3 = 14.48 mL.

Sometimes, the average volume of titrant is taken only from results that are concordant with each other
(i.e., from titer results that differ from each other by 0.20 mL or less). In this example, the average of all
the run results has been taken.

To convert a volume value in milliliters to liters, the value in milliliters is divided by 1 000 according to
this unit conversion calculation:

The mL units cancel with each other, giving a volume in liters of 0.01448 L. This titrant volume can
be used to calculate the number of moles of base.

Now, steps 1 to 3 can be followed to determine the analyte concentration.

In step 1, the number of moles of the titrant can be calculated from its concentration, which is 0.0950
mol/L, and its average volume, which is 0.01448 L:

In step 2, the number of moles of the analyte is determined by relating it to the number of moles of the
titrant from step 1 using the stoichiometric coefficients (molar ratio) from the balanced equation: 1
mole of HCl reacts with 1 mole of NaOH (from the balanced equation); therefore, 𝑥 moles of HCl will
react with 0.0013756 moles NaOH.
Then, we can solve for 𝑥:

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 CC 102: QUALITATIVE AND QUANTITATIVE CHEMISTRY
College of Liberal Arts, Sciences and Education
Prepared by: ERWIN R. ABRENCILLO, PhD
DENNIS M. DIMARANAN

In step 3, the concentration of the analyte can be calculated from its number of moles (from step 2) and
its volume, which is 20.00 mL. This volume value needs to be converted to liters, which is done in the
same manner as before, by dividing the value by 1 000:

This value can then be used with the number of moles of HCl to determine its concentration:

The concentration of the acid, in terms of molarity, is therefore 0.069 mol/L.

Calculating the Concentration of an Analyte in a Titration

Step 1: Calculate the number of moles of the titrant from its concentration and its average titer.

Step 2: Calculate the number of moles of the analyte by relating it to the number of moles of the titrant
(from step 1) using the stoichiometric coefficients from the balanced equation.

Step 3: Calculate the concentration of the analyte from its number of moles (from step 2) and its volume.

There is a simpler way to do this calculation, by combining the three steps into one step using the
following equation:

where 𝑛acid is the stoichiometric coefficient of the acid from the balanced equation and 𝑛base is the
stoichiometric coefficient of the base from the balanced equation.

When the concentration is expressed as a molarity, the symbol 𝑐 can be replaced by the symbol 𝑀and
the expression becomes

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 CC 102: QUALITATIVE AND QUANTITATIVE CHEMISTRY
College of Liberal Arts, Sciences and Education
Prepared by: ERWIN R. ABRENCILLO, PhD
DENNIS M. DIMARANAN

Example:
A 30 mL solution of nitric acid was titrated against a 0.1 M solution of potassium hydroxide. The addition
of 26.6 mL of potassium hydroxide was found to neutralize the nitric acid. What is the concentration of
the nitric acid? Give your answer to 2 decimal places.

In this titration, the analyte is the nitric acid, HNO()3aq, whose concentration is unknown but whose
volume is known to be 30 mL. The titrant is the standard solution potassium
hydroxide, KOH()aq, whose known concentration is given as a molarity of 0.1 M, which is 0.1
mol/L. The volume of the base, which is the titer, is 26.6 mL.

The balanced acid–base reaction equation is

It is convenient to write down the data in a format that makes it easy to use. One such way is to write
the data underneath the corresponding substance in the balanced equation as follows:

There are different ways to set out the solution to this problem. One way is to follow the three-step
procedure as in the diagram below:

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 CC 102: QUALITATIVE AND QUANTITATIVE CHEMISTRY
College of Liberal Arts, Sciences and Education
Prepared by: ERWIN R. ABRENCILLO, PhD
DENNIS M. DIMARANAN

Before starting step 1 of the calculation, make sure that the volume of the base is expressed in units
compatible with the base concentration units. Concentration is given in moles per liter(mol/L), so the
volume can be expressed in liters, and the unit conversion from milliliters to liters is as follows:

Now we can proceed with step 1.

Step 1: Calculate the number of moles of the base from its concentration and its volume:

Step 2: Relate the number of moles of the base to the number of moles of the acid according to the
stoichiometric coefficients (molar ratio) from the balanced equation to determine the number of moles of
acid: 1 mole of HNO3 reacts with 1 mole of KOH (from the balanced equation);
therefore, 𝑥 moles of HNO3 will react with 0.00266 moles of KOH.

We can then solve for 𝑥:

Step 3: Calculate the concentration of the acid from its number of moles (from step 2) and its volume
in liters:

The concentration of the nitric acid, in terms of molarity, is therefore 0.09 mol/L.
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 CC 102: QUALITATIVE AND QUANTITATIVE CHEMISTRY
College of Liberal Arts, Sciences and Education
Prepared by: ERWIN R. ABRENCILLO, PhD
DENNIS M. DIMARANAN

Neutralization titrations are also useful for determining the percentage of an acid or a base in a mixture.

Step 1: Calculate the number of moles of the titrant from its concentration and its average titer.

Step 2: Calculate the number of moles of the analyte by relating it to the number of moles of the titrant
(from step 1) using the stoichiometric coefficients from the balanced equation.

Step 3: Calculate the mass of the analyte from its number of moles (from step 2) and its molar mass.

Step 4: Calculate the percentage by mass of the analyte from its mass (from step 3) and the total mass
of the solid mixture.

An example is when a mixture of 1.8 g of solid Ca(OH)2 and CaCl2 is titrated against 0.25
M HCl(aq). If 25 mL of the acid is required to completely neutralize all the base in the mixture, we can
determine the percentage of base in the mixture and also the percentage of the CaCl2 salt.

First, the reaction equation needs to be balanced as follows:

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CC 102: QUALITATIVE AND QUANTITATIVE CHEMISTRY
College of Liberal Arts, Sciences and Education
Prepared by: ERWIN R. ABRENCILLO, PhD
DENNIS M. DIMARANAN

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CC 102: QUALITATIVE AND QUANTITATIVE CHEMISTRY
College of Liberal Arts, Sciences and Education
Prepared by: ERWIN R. ABRENCILLO, PhD
DENNIS M. DIMARANAN

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 CC 102: QUALITATIVE AND QUANTITATIVE CHEMISTRY
College of Liberal Arts, Sciences and Education
Prepared by: ERWIN R. ABRENCILLO, PhD
DENNIS M. DIMARANAN

Other Titration Calculation

At the equivalence point in a neutralization, the moles of acid are equal to the moles of base.

moles acid=moles base

Recall that the molarity (M) of a solution is defined as the moles of the solute divided by the liters of
solution (L). So the moles of solute are therefore equal to the molarity of a solution multiplied by the
volume in liters.

moles solute = M × L

We can then set the moles of acid equal to the moles of base.

MA × VA = MB × VB

MA is the molarity of the acid, while MB is the molarity of the base. VA and VB are the volumes of the
acid and base, respectively.

Suppose that a titration is performed and 20.70mL of 0.500M NaOH is required to reach the end point
when titrated against 15.00mL of HCl of unknown concentration. The above equation can be used to
solve for the molarity of the acid.

The higher molarity of the acid compared to the base in this case means that a smaller volume of the
acid is required to reach the equivalence point.

The above equation works only for neutralizations in which there is a 1:1 ratio between the acid and
the base. The example below demonstrates the technique to solve a titration problem for a titration of
sulfuric acid with sodium hydroxide.

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 CC 102: QUALITATIVE AND QUANTITATIVE CHEMISTRY
College of Liberal Arts, Sciences and Education
Prepared by: ERWIN R. ABRENCILLO, PhD
DENNIS M. DIMARANAN

Learning Tasks:
Solve the following problems:

1. If it takes 54 mL of 0.1 M NaOH to neutralize 125 mL of an HCl solution, what is the concentration
of the HCl?
2. If it takes 25 mL of 0.05 M HCl to neutralize 345 mL of NaOH solution, what is the concentration
of the NaOH solution?
3. If it takes 50 mL of 0.5 M KOH solution to completely neutralize 125 mL of sulfuric acid solution
(H2SO4), what is the concentration of the H2SO4 solution?
4. A standard solution of 0.25 M H2SO4 is used to determine the concentration of a 220 mL
LiOH solution. The addition of 143 mL of HSO24 resulted in complete neutralization. What is the
concentration of the LiOH solution? Give your answer in units of millimolars.
5. A 0.2 g solid mixture of KOH and KCl was titrated against a 0.1 M solution of HCl. The addition
of 20 mL of HCl resulted in complete neutralization. As a whole number, what was the
percentage of KOH in the solid mixture?

References:
Harvey, D V. (2010). Modern analytical chemistry. De Pauw University
West, D.M. (2015) Fundamentals of analytical chemistry 9th Edition

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