TYPES AND APPLICATIONS OF RADIOMETRIC

TITRATION

Submitted to: Mam Rabia Raza

Submitted by: Fatima Maqbool
Subject: Nuclear Chemistry
Roll no: 2025107041
Session: 2020-2024
Date: 20-11-2023
Contents
DEFINITION: ......................................................................................................................................... 3
PRINCIPAL: .......................................................................................................................................... 3
TYPES OF RADIOMETRIC TITRATION: .......................................................................................... 3
PRECIPITATE FORMATION RADIOMETRIC TITRATION: ........................................................ 3
Definition: ..................................................................................................................................... 3
Graphs: ......................................................................................................................................... 3
Definition: ..................................................................................................................................... 5
Explaination: ................................................................................................................................ 5
Example : ...................................................................................................................................... 5
REDOX REACTION RADIOMETRIC TIRATION: ......................................................................... 6
Definition: ..................................................................................................................................... 6
Explanation: ................................................................................................................................. 6
Example: ....................................................................................................................................... 6
RADIOMETRIC TITRATION IN NON-AQUEOUS MEDIA: .......................................................... 6
Definition: ..................................................................................................................................... 6
Explanation: ................................................................................................................................. 6
APPLICATIONS: .................................................................................................................................. 7
 Determination of structure of compounds: ....................................................................... 7
Example: ....................................................................................................................................... 7
 Investigation of co-precipitation: ......................................................................................... 7
 Determination of solubility product: ................................................................................... 7
 Determination of specific activity of radioactive preparation: ....................................... 7
DISADVANTAGES: ............................................................................................................................. 8
REFERENCES ................................................................................................................................... 10
 RADIOMETRIC TITRATION
DEFINATION:
Radiometric titration is a volumetric titration method with a special
opportunity for the indication of end-point. It can be used when titrant gives an insoluble
precipitate or a compound can be extracted easily, and when one of the reaction partners can be
labeled. During the titration, the reagent is added in different quantities and the activity of the
precipitate or filtrate is measured or, in case of extraction the activity of one phase is determined.
In short form, it is defined as
“When a titration involve the use of radioactive indicator to transfer material between two
liquid phases in equilibrium it is called RADIOMETRIC TITRATION“

PRINCIPAL:
Radiometric titrations follow the relation between the radioactivity of one
component or phase of the solution under analysis and the volume of added titrant. The
compound formed during the titration must be easily separable from the excess of unreacted
ions.

TYPES OF RADIOMETRIC TITRATION:

The following are four main types of radiometric titration:

1. Titration based upon precipitate formation

2. Titration based upon complex formation
3. Titration based upon redox titration
4. Titration based on Non-aqueous media

1. PRECIPITATE FORMATION RADIOMETRIC TITRATION:

 Definition:
“A type of radiometric titration in which the radioactive indicator is
precipitated and the end point is determined by change in the activity of solution of precipitates”

 Graphs:
In radiometric titration based on precipitate formation, three titration curves are
obtained. The shape of curve will depend upon whether the titrant, test solution or both are
labelled as radioactive. The curve is plotted between the volume of titrant and activity of
precipitate formed.
a. When the solution to be titrated is active and the titrant is inactive, the activity of the
supernatant solution shows a decrease during titration proportional to the formation
of precipitate. At the equivalence point, the actual activity of the solution is
determined by the solubility of the precipitate
𝑨𝑪 + 𝑩∗ 𝑪 → 𝑨𝑩∗ + 𝑪𝑫

Figure 1 : Titration curve between active titrated solution and inactive titrant
b. When the solution to be titrated is inactive and the titrant is active, the activity of the
solution is determined at the beginning of titration by the solubility product of the
precipitate formed during titration, and the activity does not rise until the equivalence
point is reached. However, on attaining this point, the activity of the solution increases
markedly on the addition of further portions of active titrant.
𝑨∗ 𝑪 + 𝑩𝑪 → 𝑨∗ 𝑩 + 𝑪𝑫

Figure 2 : Titration curve between inactive titrated solution and active titrant
 c. When both the titrated solution and the titrant are active, the activity of the solution
decreases during titration, and subsequently rises. The equivalence point is
determined by the minimum value of the curve.
𝑨∗ 𝑪 + 𝑩∗ 𝑪 → 𝑨∗ 𝑩∗ + 𝑪𝑫

Figure 3 : Titration curve when both solution and titrant are active

2. COMPLEXOMETRIC TITRATION :

 Definition:
“ The type of radiometric titration in which the complex is formed btween the
analyte and titrant”

 Explaination:

The end point of this tiration also depend on the activity of the solution of
complex. This type of titration require specialized indicator that form weak complex with weak
analyte. In these reactions the reacting species and the reaction products are in the same phase
,before and after the reaction. Therefore thesee titrations can only be carried out by using
auxillary methods of seperation,solvent extraction ,paper chromatography, ion-exchange etc.
 Example:
Eriochrome black T is used as an indicator for complex metric titrations because
it forms a colored complex in its protonated form with calcium, magnesium, and other metal
ions. Eriochrome black T is blue in buffered solution. When calcium or metal ions are added, the
color changes with a range of pink to red.
REDOX REACTION RADIOMETRIC TIRATION:

 Definition:
“Redox Titration are based on a reduction-oxidation reaction between
oxidizing and reducing agent. “
 Explanation:
Among the methods of titrimetric analysis, redox titrations are of great
importance because a great number of multivalent elements can be titrated successfully with an
oxidant or a reductant.In redox titration, all components are in same phase. A potentiometer or
a redox indicator is used to measure the endpoint of the titration. Some redox reactions do not
require indicator because of intense colors of the constituents.
 Example:
In permanganometry , a slight persisting pink color signal the endpoint of the
titration because of the pink color of excess of oxidizing agent potassium permanganate.

RADIOMETRIC TITRATION IN NON-AQUEOUS MEDIA:

 Definition:
“Non-aqueous titration are those titration in which titration of weak acidic or
basic substance carried out using non-aqueous substance, to get end point “
 Explanation:
This type of titration is carried out for those substances which are not
soluble in non-aqueous solvents. The sensitivity of the method is increased by using a non-
aqueous solvent in which the precipitate formed during titration is less soluble than in water. The
need for non-aqueous titration arises because water can behave as a weak base and a weak acid
as well, and can hence compete in proton acceptance or proton donation with other weak acids
and bases dissolved in it.
The non-aqueous solvents used are:

 Aprotic solvents( Neutral solvents e.g. Benzene ,chloroform )

 Protogenic solvents ( More acidic character e.g. sulphuric acid , acetic acid
 Protophilic solvents ( More basic character e.g. ammonia ,pyridine )
 Amphiprotic solvents ( protophilic and protogenic character e.g. Acetic acid, Alcohols )
APPLICATIONS:

Radiometric titration is a powerful analytical technique that has found

numerous applications across various fields. Its ability to detect and measure trace amounts of
analytes with high accuracy and selectivity makes it an invaluable tool for a wide range of
analytical challenges. Here are some of the key applications of radiometric titration:

 Determination of structure of compounds:

During radiometric titration, various compounds are formed so their
composition can be determined.
o Example:
The composition of solutions of silver and cobalt tungstate has been studied
by Bradhurst, Coller and Duncana at various pH values, using radiometric titrations. On titrating
a solution of sodium tungstate at pH 6.2-7.8 with a silver nitrate solution labelled with 𝐴110 , a
titration curve with a sharp break is obtained. The ratio Ag: W can easily be calculated from the
end-point.
 Investigation of co-precipitation:
Co-precipitation of various labelled compounds has been
investigated, using radiometric titration, by Aiimarin and Sirotina, who studied in detail the co-
precipitation of 𝑇𝐼 204 with𝐴𝑔𝐼, 𝐴𝑔𝐶𝐹, 𝐴𝑔𝑆𝐶𝑁 and 𝑃𝑏𝐼 precipitates, the titration of silver and
thallium with𝑇𝑙𝐼 204 , and that of lead and silver with𝐶𝑟𝑂−2 .

 Determination of solubility product:

A method has been evolved by Duncan 87 for the
determination of solubility product by radiometric titration. He derived an equation that
involves R (radioactivity) and v (volume of solution), The titration curve actually reflects the
changes of R plotted against v. With the aid of equation, it is possible to calculate the value
of S from any point along the curve.

 Determination of specific activity of radioactive preparation:

Kametanietal have been studied the use of radiometric
titration in the determination of specific reactivity of preparations.
ADVANTAGES:

 Detection point does not depend upon the chemical reaction unlike the normal titration
where indicator precipitate in reaction

 . Radiometric titration is highly sensitive. Radiometric titration can be used to detect very
small amounts of analyte, making it a valuable tool for trace analysis.

 Radiometric titration are versatile as they can be used for a wide variety of titrations,
including precipitation, complexation, and redox reactions.

 Radiometric titration is specific for the analyte being titrated, as the radioactivity is
associated only with the analyte.

 Radiometric titration provides quantitative data, making it valuable for precise

concentration measurements.

DISADVANTAGES:

 Phase separation method: there is requirement of phase separation method as it is not

automated as in precipitation method.
 The need for radioactive isotopes: Radioactive isotopes are expensive and require special
handling and disposal procedures.
 Limited availability of equipment: Radiometric titration equipment is not as widely
available as conventional titration equipment.
 Radiation Exposure and Safety Concerns:
o One of the primary disadvantages of radiometric titration is the inherent use of
radioactive materials. Working with these materials poses potential health risks
due to radiation exposure.
o Stringent safety protocols, protective equipment, and specialized training are
required to minimize the risk to laboratory personnel.

 Instrumentation Complexity:
o Radiometric titration often requires sophisticated and complex instrumentation,
including detectors and counters capable of measuring different types of radiation
(beta, gamma, or alpha).
 o The setup and operation of such equipment can be challenging, demanding skilled
personnel and regular maintenance.
 Cost of Equipment:
o Acquiring and maintaining the specialized equipment needed for radiometric
titration can be costly. This cost can be a limiting factor for smaller laboratories or
those with budget constraints.
o Regular calibration and quality control of the equipment are essential, adding to
the overall expenses.
 Limited Isotope Availability:
o Some isotopes suitable for radiometric titration may have limited availability. This
constraint can restrict the range of applications or require reliance on alternative
methods when specific isotopes are not readily accessible.
 Quenching Effects:
o Quenching refers to the reduction in the intensity of the emitted radiation due to
interactions with the sample matrix or other substances present.
o Quenching effects can complicate measurements, leading to inaccuracies in the
titration results. Addressing quenching often requires additional sample
preparation steps.
 Waste Disposal Challenges:
o Dealing with radioactive waste generated during radiometric titration poses
challenges. Proper disposal methods and adherence to regulatory guidelines are
essential to mitigate environmental impact and ensure safety.
 Limited Selectivity:
o Radiometric titration may lack the selectivity to distinguish between different
chemical species if they emit similar types of radiation.
o Selectivity issues can be a limitation when dealing with complex sample matrices
containing multiple isotopes or compounds.
 Sample Size Requirements:
o Some radiometric titration techniques may require relatively large sample sizes,
which could be a limitation when dealing with precious or limited-volume
samples.
REFERENCES :

 Braun, Tibor & Tolgyessy, J. (1964). Radiometric Titrations. Talanta. 11. 1277-1312.
10.1016/0039-9140(64)80186-7.

 Analytical applications (Radiometric titration). (n.d.). Retrieved November 19, 2023,

from https://www.bcp.fu-

berlin.de/chemie/chemie/forschung/InorgChem/agabram/pdf/radiochemie/07_radi

oenglish.pdf

 radiometric titrations. (2016, November 17). Www.slideshare.net.

https://www.slideshare.net/MadanLal33/radiometric-titrations

 (Radiometric Titration (Radiotracer Techniques), n.d.)