Name: Abdullah Tariq

Roll number: bpd02183389

Volumetric analysis was initiated for the first time by French chemist Jean
Baptiste André Dumas. It is a mode of quantitative analysis which is based on the
determination of the volume of a solution of known concentration (standard)
required to react quantitatively with a solution of the substance to be analysed. It
is also known as titrimetric analysis.
There are many different types of titrations that differ by the titrant used and
substances that can be determined. While every titration is different, they all
share similar characteristic - but before we will start to discuss them let's define
several important terms.
 Titrate: The Substance to be analysed is called titrate.
 Titrant: The reagent of known concentration which is added to the
solution of the substance to be analyzed is called titrant.
 Titration Curve: A plot of solution pH versus titrant volume during a
titration.
 Titration: The process of finding out the volume of the titrant required
to react completely with a known volume of solution (Titrate) under
analysis is known as titration.
 Indicator: Auxiliary agents used to determine the end point of titration.
A species added to the analyte to give an observable change at (which is
the endpoint) or near the end point.
 End Point: The end point is the point where the system changes when
the moles of the reacting titrant exceed the moles of the substance
being titrated. When using an indicator, the end point occurs when
enough titrant has been added to change the colour of the indicator.
 Equivalence Point: The equivalence point is the exact point in a titration
when the moles of titrant equal the substance being titrated.
 Titration Flask: In volumetric analysis, two solutions are always made to
react in a conical flask known as titration flask.
 Standard Solution: It is a solution of definite concentration or of known
strength.
  Standardization: It is a process whereby the concentration of a solution
is determined by the known concentration of solution.
 Titration Error: It is the smallest difference between equivalence point
and end point. This difference is because an indicator always produces
the visual change either a little before or after the equivalence point.
THE BASIC PRINCIPLES OF VOLUMETRIC ANALYSIS
 The one solution to be analyzed contains an unknown amount of
chemicals.
 The reagent of known concentration reacts with chemical of unknown
amount in the presence of an indicator to show the endpoint. This is the
point which shows the completion of the reaction.
 The volumes are measured by a titration which completes the reaction
between reagent and solution.
 The volume and concentration of reagent used in the titration give the
amount of reagent in moles.
 The amount of unknown chemical in the measured volume of solution is
calculated by using the mole ratio of the equation.
 The amount of unknown chemical in the original sample is calculated by
the amount of unknown chemical in the measured volume.

TYPES OF TITRATIONS
Based on the nature of solvents and chemical reaction:
The titrimetry can be categorized into four types which are based on the type of
reaction involved in the process.
ACID-BASE TITRATIONS
The strength of an acid can be determined using a standard solution of base is
called as acidimetry. In the same way, the strength of a base can be found with
the help of standard solution of an acid is known as alkalimetry. The acid- base
titration is based on the reaction that neutralization between a base or an acidic
and analyte.
An acid-base titration is a procedure used in quantitative chemical analysis to
determine the concentration of either acid or a base.
• The equivalence of an acid-base titration is the point at which there are
equal amounts (in moles) of H3O and OH in titration flask.
• Endpoint of titration - the point in a titration at which the indicator changes
colour.
• The indicator should change color sharply at the equivalence point.
• At the end point of the titration, all the acid has been neutralized by the
alkali the solution in the conical flask contains salt and water only.
ACID-BASE INDICATORS
• Acid base indicators are weak organic acids that dissociate slightly in
aqueous solutions to form ions.
• The indicators can change color because their ions have colors that are
different from undissociated molecule.
PHARMACEUTICAL APPLICATIONS OF ACID-BASE TITRATION
▪ Many pharmaceutical compounds are weak acids or bases that can be
analyzed by an aqueous or no aqueous acid-base titration; examples
include salicylic acid, phenobarbital, caffeine and sulfanilamide.
▪ Amino acids and proteins can be analyzed in glacial acetic acid, using HCIO4
as the titrant. For example, a procedure for determining the amount of
nutritionally available protein has been developed that is based on an
acidbase titration of lysine residues.
▪ Acid-base titrimetry is a standard method for the quantitative analysis of
many inorganic acids and bases.
▪ Standard solutions of NaH can be used in the analysis of inorganic acids
such as Phosphoric acid (H3P04) or Arsenic acid (H3As04), whereas
standard solutions of HCl can be used for the analysis of inorganic bases
such as Na2C03.
▪ It is used in the analysis of caffeine and saccharin in pharmaceutical
products as well as for the analysis of proteins, fertilizers, etc.

REDOX TITRATIONS
The redox titration is also known as an oxidation-reduction reaction. In
this type of titration, the chemical reaction takes place with a transfer of
electrons in the reacting ions of aqueous solutions.
Redox titration is based on an oxidation-reduction reaction between
the titrant and the analyte. It is one of the most common laboratory
methods to identify the concentration of unknown analytes.
REDUCTION
A substance can undergo reduction can occur via:
 The addition of hydrogen.
 The removal of oxygen.
  The acceptance of electrons.

OXIDATION
The following points describe a substance that has undergone oxidation.
 The addition of oxygen.
 Removal of hydrogen which was attached to the species.
 The donation/loss of electrons.
 An increase in the oxidation state exhibited by the substance.
Thus, it can be understood that redox titrations involve a transfer of
electrons between the given analyte and the titrant. An example of a
redox titration is the treatment of an iodine solution with a reducing
agent. The endpoint of this titration is detected with the help of a starch
indicator.
REDOX TITRATION EXAMPLE
An example of a redox titration is the titration of potassium
permanganate against oxalic acid.
PRECIPITATION TITRATIONS
The titration is based on the insoluble precipitate formation when the two
reacting substances are brought into contact are called as precipitation
titration.

METHODS
Different methods involved in argentometrx;
 Mohr's method
 volhard's method
 Fajan's method
USE
Determine the content of Chloride and Bromide.
PRINCIPLE
Using Chromate indicator NaCl + AgNO3? AgCI (precipitate) + NaN03
2AgNO3 + K2Cr04 (precipitate) + 2KN03

CONCLUSION
 Titrations with Ag+ are called argentometric titrations.
 For argentometric titrations, three classical methods based on colour
indicators can be used for end point detection.
 Mohr titration - formation of colored precipitate at the end point.
 volhard titration - formation of a soluble, colored complex at the end
point.
 Fajans titration - adsorption of a colored indicator on the precipitate
at the end point
COMPLEXOMETRIC TITRATIONS:
This type of titration is like precipitation titration in that a solid precipitates
out of the sample when a reagent is added. The difference is that in
complexometric titration, the solid is formed more quickly and more
completely than in precipitation titration, which reduces errors in
measurement. Ethylenediaminetetraacetic acid, an acidic powder better
known as EDTA, is commonly used in this type of titration because it readily
bonds with metals. This type of titration can be used to measure the
ingredients within soaps and detergents.
Complexometric Titration or chelatometric is a type of volumetric analysis
wherein the coloured complex is used to determine the endpoint of the
titration.
Complexometric Titration is in the detection of mixtures of different metal
ions present in the solution.
 When each drop of titrant is added, the reaction reaches an
equilibrium state swiftly. There would be no chance for any
interfering situations.
  The equivalent point can be identified very accurately using
complexometric titration. EDTA is used as a titrant and it is pretty
much well established.

INDICATORS
Calmagite, and Erichrome BlackT (EBT) are such indicators that change from
blue to pink when they complex with calcium or magnesium. The endpoint
of a complexometric EDTA titration using either Calmagite, or EBT as the
indicator is detected as the colour changes from pink to blue.

END POINT DETECTION

The endpoint detection in complexometric titration can be done by two
methods.

Visual Method
One of the most common methods for determination of endpoint owing to
its simplicity, least cost and accuracy. Following are some of the visual
which is competed with in an aqueous solvent by the reaction given by:
HO+H* = 430*
This type of competition provided by water towards weak bases or weak
acids makes it difficult to detect the end point of the titration. Therefore,
these substances which have very sharp end points when titrated in
aqueous solutions due to their weakly basic or weakly acidic nature
generally need to be titrated in non-aqueous solvents.
• Many reactions which occur in non-aqueous titration procedures can
be explained via the Bronsted-Lowry, Theory and its definition of acids
and bases. Basically, acids can be thought of as proton donors,
whereas bases can be thought of as proton acceptors.
• The potentially acidic substances can behave as acids only when a
base (to which a proton can be donated) is present, i.e. potentially
basic substances can behave as bases only when an acid (from which a
proton can be accepted) is present.

BASED ON METHOD OF TITRATION

They are of three types of titrations based on the method used in process of
titration.

1.DIRECT TITRATION
As the name indicates, it is basic titration. In this method, the solution of
the substance to be determined quantitatively is directly titrated with a
suitable titrant by using an appropriate indicator or a suitable instrument to
locate the end point.
Example: The titration of strong acids such as HNO3, H2SO4, HCl, etc. with
strong alkalis such as NaOH, KOH.

2. IN-DIRECT TITRATION
Theoretically it is converting a substance into an acid and analysing with a
base (also vice-verse). This is a method extrapolated to use titration for
non-readily reactive substances. A substance can be weakly acidic and so it
does not permit for precise analysis by direct titration. So first that
substance is chemically altered to be more reactive in acidic or basic form
and then analyzed by adding a titrant.

3.BACK TITRATION
This titration is followed when the direct titration is not possible. For
example, the reaction between determined substances and titrant can be
too slow, or there can be a problem with end point determination. In this
method, the substance to be analyzed is dissolved in a known sufficient
volume of a standard solution of acid or alkali. The excess of acid or alkali
remaining in the solution is back titrated by using suitable indicator. A blank
determination (without substance) is done from which the difference is the
volume required for the substance is found out.
Back titrations are used when:
➢ One of the reactants is volatile, for example ammonia.
➢ An acid or a base is an insoluble salt, for example calcium carbonate.
➢ A particular reaction is too slow.
Direct titration of weak acid/base: the end point is very difficult to observe.
METHODS TO DETERMINE THE ENDPOINT
➢ . pH indicator: This is a substance which shows the chemical change
by changing the color.
➢ A potentiometer: This is used to measure the electrode potential of
the solution. These are used for redox titration. They show the end
point with changing potential of the working electrode.
➢ pH meter: It is a ion-selective electrode. In pH meter the potential of
electrode depends on the amount of H+ ion present in the solution.
The pH of the solution can be measured in the whole titration. This
gives more correct result than indicators.
➢ Conductance: The conductivity of solutions is also changed in
titration, and it depends on the ions present in the solution, mobility
of ions and ions concentration.

➢ Color change: In the redox reactions, the color of solution changes

without use of indicator. This is due to different oxidation states of
the product.

➢
PRIMARY AND SECONDARY STANDARDS
Standards: The solution whose concentration is exactly known is called
standard solution. Standards are materials containing a precisely known
concentration of a substance for use in quantitative analysis. A standard
provides a reference that can be used to determine unknown
concentrations or to calibrate analytical instruments. There are two types of
standard solutions used in volumetric analysis. They are:
1. Primary Standard
2.Secondary Standard

PRIMARY STANDARD
From the name itself it is obvious that this is a standard which comes first.
That’s why the name is primary.
A primary standard is a chemical or reagent which has certain properties
such as:
 It is extremely pure,
 Highly stable
 It is anhydrous
 It’s less hygroscopic
 Has very high molecular weight
 ➢ Can be weighed easily
➢ Sh ould be ready to use and available
➢ Should be preferably nontoxic
➢ Should not be expensive

S OME OF THE EXAMPLES FOR PRIMARY STANDARDS

1. ACID-BASE TITRATIONS
• Sodium Carbonate (Anhydrous)

• Potassium Hydrogen Phthalate

• Oxalic acid
2. REDOX TITRATIONS
• Potassium Dichromate

• Potassium Bromate

• Potassium Iodate

• Oxalic acid

• Arsenic Trioxide
3. PRECIPITATION TITRATIONS
• Silver Nitrate
4. COMPLEXOMETRIC TITRATIONS
• Pure Metallic Zinc

• Zinc Chloride

S ECONDARY STANDARD
A secondary standard is a substance which may be used for
standardizations, and whose content of the active substance has been
found by comparison against a primary standard. A secondary standard is
used by standard laboratories such as companies involved in preparation
of reagents, kits or laboratories responsible for producing quality control
material for other labs. Secondary standard is used for th e purpose of
calibration of control material in smaller lab for analysis of unknown
concentration of a substance. So basically, secondary standard serves the
purpose of external quality control for smaller labs. This makes it essential
that the secondary standard must first be standardized against the primary
standard.
A secondary standard is a chemical or reagent which has certain properties
such as
 It has less purity than primary standard
 Lessstableandmorereactivethanprimarystandard
 But its solution remains stable for a long time
 Titrated against primary standard

Usually, a chemical fit for being a standard chemical yet does not meet the
requirements of a primary standard.
The best example is anhydrous sodium hydroxide. It is extremely
hygroscopic. As soon as the bottle is opened sodium hydroxide starts
absorbing moisture from atmosphere and within no time it becomes moist.
So, sodium hydroxide cannot be used as a primary standard for the reason
that it absorbs water and carbon dioxide from the atmosphere and the
composition of its solution is subject to wide variations at different periods.

METHODS OF EXPRESSING CONCENTRATION OF SOLUTION

In chemistry, a solution is a homogeneous mixture composed of only one
phase. It’s either solid, liquid or a gas. The solubility of a solute is the
amount of solute that will dissolve in each amount of solvent at particular
temperature to produce a saturated solution.
Solute: A substance dissolved in another substance, usually the component
of a solution present in the lesser amount.
Solvent: A substance in which another substance is dissolved, forming a
solution. The concentration of a solution is a macroscopic property,
represents the amount of solute dissolved in a unit amount of solvent or of
solution, and can be expressed in a variety of ways (qualitatively and
quantitatively).
 1. Qualitative Expressions of Concentration
2. Semi-Quantitative Expressions of Concentration
3. QuantitativeExpressionsofConcentration

QUALITATIVE EXPRESSIONS OF CONCENTRATION

A solution can be qualitatively described as:
Dilute: A solution that contains a small proportion of solute relative to
solvent.
Concentrated: A solution that contains a large proportion of solute relative
to solvent.
SEMI-QUANTITATIVE EXPRESSIONS OF CONCENTRATION
A solution can be semi-quantitatively described as:
Unsaturated: A solution in which more solute will dissolve Saturated:
A solution in which no more solute will dissolve

QUANTITATIVE EXPRESSIONS OF CONCENTRATION

There are several ways to express the relative amounts of solute and
solvent in a solution. Which one we choose to use often depends on
convenience. For example, it is sometimes easier to measure the volume of
a solution rather than the mass of the solution.
Note that some expressions for concentration are temperature-dependent
(i.e., the concentration of the solution changes as the temperature
changes), whereas others are not. This is an important consideration for
experiments in which the temperature does not remain constant.

1. PERCENTAGE
It refers to the amount of the solute per 100 parts of the solution. It can also
be called as parts per hundred (pph). It can be expressed by any of following
four methods,
Mass Percentage [% w/w]: When the concentration is expressed as the
percent of one component in the solution by mass it is called mass
percentage. It is defined as the amount of solute in grams present in 100
grams of the solution
Volume Percentage

[ % v/v ]: It is defined as the v olume of solute in mL present in 100 mL

solution. Sometimes we express the concentration as a percent of one
component in the solution by volume, it is then called as volume
percentage and is given as:
Mass by Volume Percentage: It is defined as the mass o f solute present in
100 mL of solution.

2 . PARTS PER MILLION (PPM) AND PARTS PER BILLION (PPB)

When a solute is present in trace quantities, it is convenient to express the
concentration in parts per million and parts per billion. It is the number of
parts of solute per million or per billion parts of the solution. It is
independent of the temperature.

3 .STRENGTH
The strength of solution is defined as the amount of solute in grams
present in one litre (or) of the solution. It is expressed in g/litre.

4 .MOLARITY (M )
It is defined as the numb er of moles of solute per litter of solution.
Molarity = no. of moles of solute/volume of solution litters
Note that molarity is spelled with an "r" and is represented by a capital M.

5 .MOLALITY (M )
It is defined as the number of moles of solute per kilogram of solvent.
M olality = no. of moles of solute/mass of solvent in kg

NORMALITY (N)
It is defined as the number of gram equivalents (equivalent
weight in grams) of a solute present per litter of the solution. Normality
changes with
temperature since it involves volume. Gram equivalent weight is the
measure of the reactive capacity of a molecule.
Solutions in term of normality generally expressed as,

MOLE FRACTION: The mole fraction of one component in a solution is

defined as: the number of moles of that component divided by the total
number of moles of all components in the solution.
It is denoted by the symbol X.