MCH-004

Electroanalytical and Other Methods

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MCH-004
Course Code: MCH-004
Assignment Code: MCH-004/TMA/2024
Maximum Marks: 100
Note: Answer all the questions given below.

Q.1 a) What do you understand by cell potential? Calculate the potential of following electrodes: (5)
i) A copper electrode immersed in 0.022 M Cu(NO3)2

ii) A zinc electrode immersed in 0.030 M Zn(NO3)2.

b) Describe various factors that cause errors in pH measurement. (5)

Q.2 a) What is solid state membrane electrode? Draw a sketch diagram and describe their
applications. (5)

b) Define conductivity, cell constant and molar conductivity. Resistance of a conductivity cell filled
with 0.1M KCl solution is 100 Ω. If the resistance of the same cell when filled with 0.02 M KCl solution
is 520 Ω, calculate the conductivity and molar conductivity of 0.02 M KCl solution. The conductivity of
0.1 M KCl solution is 1.29 S m-1. (5)

Q.3 a) How will you analyse a binary alloy of copper and silver thermogravimetrically. (5)

b) A solution of CuSO4 is electrolysed for 10 minutes with a current of 1.5 amperes. What is the mass
of copper deposited at the cathode? (5)

Q.4 a) Explain how will you determine dissociation constant of a weak acid or base by
conductometric method? (5)

b) The conductivity of 0.001028 M acetic acid is 4.95 × 10-5 S cm-1. Calculate its (5) dissociation
constant if the limited molar conductivity for acetic acid is 390.5 S cm2 mol-1 .

Q.5 a) Describe the design and principle of constant current coulometry. Write three main
applications of coulometric titrations. (5)

b) Enlist various voltammetric methods of analysis. Write briefly about anodic stripping
voltammetry(ASV) and its usefulness for trace elemental analysis. (5)

Q.6 a) Explain the terms limiting current, migration current, diffusion current, residual current and
half wave potential. (5) b) What is dropping mercury electrode? Give its advantages. (5)

Q.7 a) What are amperometric titrations? Draw common types of curves obtained in amperometric
titrations. Briefly discuss their experimental set up. (5)

b) List the factors affecting TG curve. Taking a suitable example, explain the effect of furnace
atmosphere on TG curve. (5)

Q.8 a) Draw a labeled diagram of the TG curve obtained by heating a mixture of 50 mg of calcium
oxalate monohydrate and 50 mg of barium oxalate monohydrate to 1200°C. Calculate the amount of
all mass losses. (5)

b) Explain the basic principle of Differential Scanning Calorimetry (DSC). Draw a block diagram of DSC
instrument. (5)

Q.9 a) Describe various types of neutron sources available for NAA. Which one of these is most
suitable for trace element analysis? (5)

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b) In what respects nuclear reactions are different from chemical reactions? Calculate Q value of the
reaction 63Cu = (n, γ)64Cu. Give that 63Cu = 62.929590, 64Cu = 63.929760, n =1.008665 amu. (5)

Q.10 a) Explain why (n, γ) reaction is most suited for NAA. (5)

b) Discuss the principle of isotope dilution technique (5)

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Q.1 a) What do you understand by cell potential? Calculate the potential of following electrodes:

i) A copper electrode immersed in 0.022 M Cu(NO3)2

Ans:Cell Potential

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ii) A zinc electrode immersed in 0.030 M Zn(NO3)2.

Ans:

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b) Describe various factors that cause errors in pH measurement.

Ans:

Factors Causing Errors in pH Measurement

Accurate pH measurement is crucial in various scientific and industrial applications, but several
factors can introduce errors into pH readings:

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1. Electrode Condition: The condition of the pH electrode significantly affects accuracy. Electrodes
can become contaminated, fouled, or worn over time, leading to erroneous readings. Proper
maintenance and regular calibration are essential to ensure reliable results.

2. Calibration Errors: pH meters must be calibrated with standard buffer solutions of known pH.
Inaccurate calibration, whether due to using outdated or incorrect buffers, or improper calibration
procedures, can cause significant errors in pH measurement.

3. Temperature Effects: pH measurements are temperature-dependent. Most pH meters compensate

for temperature variations, but if the temperature compensation is not properly set or if the sample
temperature deviates significantly from calibration conditions, the pH readings can be incorrect.

4. Sample Contamination: Contaminants in the sample, such as oils, salts, or other chemicals, can
interfere with pH readings. This can happen if the sample comes into contact with the electrode or if
the sample is not properly prepared.

5. Electrode Slope and Response Time: The electrode’s slope (which indicates its responsiveness to
pH changes) and response time can affect accuracy. A slope that deviates from the expected 59.1 mV
per pH unit indicates potential problems, such as electrode degradation or improper calibration.

6. Interference from Ionic Strength: In very dilute or very concentrated solutions, the ionic strength
can affect the accuracy of the pH measurement. Electrodes may not perform well in such extreme
conditions, leading to errors.

7. Sample Matrix Effects: The composition of the sample matrix, including factors such as viscosity or
the presence of complexing agents, can influence electrode performance and pH readings.

To minimize errors, ensure regular calibration, proper electrode maintenance, and account for
temperature variations and sample matrix effects.

Q.2 a) What is solid state membrane electrode? Draw a sketch diagram and describe their
applications.

Ans:

Solid State Membrane Electrode

A solid state membrane electrode is an electrochemical sensor used to measure the concentration of
ions in a solution. It employs a solid-state ion-selective membrane to separate the electrode from the
sample. Unlike liquid junction electrodes, solid state electrodes use a solid material as the sensing

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element, which interacts with specific ions in the sample solution to produce a measurable electrical
signal.

Structure

1. Solid-State Membrane: Typically made from a crystalline material, such as an ion-selective glass or
a conductive polymer. The membrane selectively interacts with the target ion.

2. Reference Electrode: Usually a part of the electrode assembly, providing a stable reference
potential.

3. Internal Solution: Often contains a specific ion or electrolyte to maintain a stable internal
environment.

Sketch Diagram

Applications

1. pH Measurement: Solid state membranes, such as those made from glass, are used in pH
electrodes. The membrane's response to hydrogen ions allows for precise pH measurements in
various applications, including laboratory experiments and industrial processes.

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2. Ion Selective Measurements: For detecting specific ions like fluoride, nitrate, or potassium in
solutions. Solid state electrodes are utilized in environmental monitoring, water quality analysis, and
clinical diagnostics.

3. Industrial Processes: In industries, solid state membrane electrodes are used to monitor and
control the concentration of ions in process solutions, ensuring optimal conditions and product
quality.

4. Medical Diagnostics: They are employed in medical devices to measure ion concentrations in
bodily fluids, aiding in diagnostic and therapeutic processes.

Solid state membrane electrodes are valued for their stability, durability, and ability to provide
accurate measurements in various environmental conditions.

b) Define conductivity, cell constant and molar conductivity. Resistance of a conductivity cell filled
with 0.1M KCl solution is 100 Ω. If the resistance of the same cell when filled with 0.02 M KCl
solution is 520 Ω, calculate the conductivity and molar conductivity of 0.02 M KCl solution. The
conductivity of 0.1 M KCl solution is 1.29 S m-1.

Ans:

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Q.3 a) How will you analyse a binary alloy of copper and silver
thermogravimetrically.
Ans:
Thermogravimetric Analysis (TGA) of a Binary Copper-Silver Alloy
Thermogravimetric Analysis (TGA) is a technique used to measure changes in the
mass of a sample as it is heated, cooled, or held at a constant temperature. For
analyzing a binary alloy of copper and silver, TGA can provide insights into the
thermal stability, composition, and phase transitions of the alloy. Here’s a step-
by-step approach:
1. Sample Preparation
 Sample Size: Obtain a representative sample of the copper-silver alloy.
Typically, a small amount (a few milligrams) is sufficient for TGA.
 Sample Form: Ensure the sample is in a suitable form (e.g., powder or
small chunks) to fit into the TGA apparatus.
2. Instrument Calibration
 Calibration: Calibrate the TGA instrument using standard materials with
known thermal properties to ensure accurate measurements.

4. Data Analysis
 Mass Loss: Analyze the TGA curve, which plots mass loss against
temperature. Peaks or inflections in the curve can indicate phase
transitions, decomposition, or the formation of new compounds.
 Phase Identification: Compare the observed thermal behavior with known
phase diagrams and thermal properties of copper and silver. Look for

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temperature ranges corresponding to alloy melting points, phase

separation, or oxidation processes.
 Quantitative Analysis: Use the mass loss data to estimate the composition
of the alloy if phase transitions or decomposition reactions are well
understood. For instance, if the alloy decomposes into copper and silver
oxides, the amount of mass loss can provide clues about the alloy’s
composition.
5. Interpretation
 Phase Transitions: Identify and interpret phase transitions, such as melting
or alloy formation, based on the thermal data.
 Composition Analysis: If the alloy shows distinct mass loss patterns,
correlate these with the known properties of copper and silver to deduce
the relative proportions of each metal in the alloy.
Summary
By employing TGA, you can effectively analyze a binary copper-silver alloy's
thermal properties, phase transitions, and composition. This method helps in
understanding the thermal behavior of the alloy and aids in the characterization
of its physical and chemical properties.
b) A solution of CuSO4 is electrolysed for 10 minutes with a current of
1.5 amperes. What is the mass of copper deposited at the cathode?
Ans:

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Q.4 a) Explain how will you determine dissociation constant of a weak

acid or base by conductometric method?
Ans:

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Summary
The conductometric method involves measuring the conductivity of a solution
during titration to determine the dissociation constant of a weak acid or base. By
analyzing the changes in conductivity and the volume of titrant added, the
dissociation constant can be calculated, providing insights into the strength and
behavior of the acid or base in solution.

b) The conductivity of 0.001028 M acetic acid is 4.95 × 10-5 S cm-1. Calculate its (5) dissociation
constant if the limited molar conductivity for acetic acid is 390.5 S cm2 mol-1 .
Ans:

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Q.5 a) Describe the design and principle of constant current coulometry. Write three main
applications of coulometric titrations.
Ans: Constant Current Coulometry: Design and Principle

Design:

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Constant current coulometry involves a setup where a constant electric current is applied to drive an
electrochemical reaction. The essential components include:

1. Electrolytic Cell: Contains two electrodes—anode and cathode—immersed in an electrolyte

solution.

2. Power Supply: Provides a stable, constant current.

3. Electrochemical Cell: Measures the potential and monitors the reaction progress.

4. Counter Electrode: Completes the circuit and facilitates the current flow.

Principle:

In constant current coulometry, a fixed current is passed through the cell, and the total charge (Q)
required for a complete reaction is measured. The charge is the product of the current (I) and time
(t), given by:

Applications of Coulometric Titrations

1. Determination of Water Content: Widely used for measuring trace amounts of

water in pharmaceuticals, chemicals, and food products via Karl Fischer titration.
2. Analysis of Redox Reactions: Useful for determining the concentration of oxidizing
or reducing agents in solutions, which is crucial in various chemical and
pharmaceutical industries.
3. Purity Analysis: Employed in the quality control of metals and other substances,
ensuring that materials meet specified purity levels by quantifying the amount of
impurities through electrochemical methods.

Applications of Coulometric Titrations

1. Determination of Water Content: Widely used for measuring trace amounts of

water in pharmaceuticals, chemicals, and food products via Karl Fischer titration.

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2. Analysis of Redox Reactions: Useful for determining the concentration of oxidizing

or reducing agents in solutions, which is crucial in various chemical and
pharmaceutical industries.
3. Purity Analysis: Employed in the quality control of metals and other substances,
ensuring that materials meet specified purity levels by quantifying the amount of
impurities through electrochemical methods.

b) Enlist various voltammetric methods of analysis. Write briefly about anodic stripping
voltammetry(ASV) and its usefulness for trace elemental analysis.
Ans: ### Voltammetric Methods of Analysis

Voltammetry encompasses several electrochemical techniques for analyzing substances by

measuring current as a function of applied potential. Key voltammetric methods include:

1. **Linear Sweep Voltammetry (LSV)**: Measures current as a function of a linearly changing

potential.

2. **Cyclic Voltammetry (CV)**: Involves sweeping the potential linearly back and forth, providing
information on redox processes and kinetics.

3. **Differential Pulse Voltammetry (DPV)**: Uses superimposed pulses on a linear sweep to

enhance sensitivity and resolution.

4. **Square Wave Voltammetry (SWV)**: Applies a square wave potential modulation, improving
sensitivity and resolution for detecting low concentrations.

5. **Anodic Stripping Voltammetry (ASV)**: Combines pre-concentration and stripping steps to

detect trace elements.

6. **Cathodic Stripping Voltammetry (CSV)**: Similar to ASV but focuses on reduction reactions.

### Anodic Stripping Voltammetry (ASV)

**Principle:**

ASV involves two main steps:

1. **Pre-concentration**: The analyte is deposited onto the working electrode by reducing it from a
solution containing the analyte (usually at a constant potential).

2. **Stripping**: The deposited analyte is oxidized by sweeping the potential positively, generating a
current that is proportional to the amount of analyte.

**Process:**

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- During the pre-concentration step, the electrode is held at a potential where the analyte is reduced
and deposited.

- In the stripping step, the potential is swept in the positive direction, and the current peak
corresponds to the oxidation of the analyte.

**Usefulness for Trace Elemental Analysis:**

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ASV is highly effective for trace elemental analysis due to its high
sensitivity and low detection limits. The technique allows for the
quantification of trace metals in complex matrices by concentrating the
analyte on the electrode, which enhances the signal-to-noise ratio. This
makes ASV ideal for detecting low concentrations of metals in
environmental samples, pharmaceuticals, and food products. Its ability to
achieve sub-part-per-billion detection limits makes it valuable for
regulatory and quality control applications
. Q.6 a) Explain the terms limiting current, migration current,
diffusion current, residual current and half wave potential.
Ans: ### Key Electrochemical Terms

1. **Limiting Current:**
The limiting current is the maximum current observed in an
electrochemical system when the rate of the electrochemical reaction is
controlled solely by the rate at which the reactant reaches the electrode
surface. It occurs when the diffusion layer around the electrode becomes
fully saturated with the reactant, and further increases in potential do not
lead to an increase in current. This is often observed in techniques like
linear sweep voltammetry and cyclic voltammetry. The limiting current (\
(i_{lim}\)) is crucial for characterizing the diffusion characteristics and the
concentration of the analyte.

2. **Migration Current:**
Migration current arises from the movement of ions in an electric field,
separate from the diffusion process. When an electric field is applied, ions
migrate towards the electrode due to their charge, contributing to the
total current. Migration current is significant in high-concentration
solutions where the ionic mobility impacts the overall current response. In
dilute solutions, diffusion current usually dominates.

3. **Diffusion Current:**
Diffusion current is the component of the current due to the diffusion of
electroactive species from the bulk solution to the electrode surface. It
occurs because the analyte is transported to the electrode by
concentration gradients. The diffusion current (\(i_d\)) depends on the
concentration gradient and the rate of diffusion of the analyte.

4. **Residual Current:**
Residual current, also known as background current, is the current
measured in the absence of any electroactive species or during a baseline
scan. It includes contributions from non-faradic processes like capacitive
charging, noise, or impurities. Residual current serves as a baseline
against which faradic current changes are measured.

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5. **Half-Wave Potential:**
The half-wave potential (\(E_{1/2}\)) is the potential at which the current
reaches half of its maximum value (limiting current) in a voltammetric
experiment. It provides critical information about the redox potential of
the electroactive species and is used to identify and characterize different
substances based on their electrochemical behavior.

Understanding these terms helps in interpreting voltammetric data and

optimizing electrochemical experiments.
b) What is dropping mercury electrode? Give its advantages.
Ans: ### Dropping Mercury Electrode (DME)

**Definition:**

The Dropping Mercury Electrode (DME) is a type of electrochemical working electrode used in
various electrochemical analyses, particularly in polarography and voltammetry. It consists of a small
reservoir that continuously supplies a droplet of mercury to the electrode surface. The mercury
drops at regular intervals from a capillary tube, creating a fresh, clean electrode surface with each
droplet.

**Advantages of Dropping Mercury Electrode:**

1. **Fresh Electrode Surface:** Each new mercury drop provides a fresh surface for the
electrochemical reaction, reducing the likelihood of surface contamination and ensuring consistent
electrode performance throughout the analysis.

2. **High Sensitivity:** The DME offers excellent sensitivity due to the large surface area of the
mercury drop compared to other types of electrodes. This makes it particularly effective for detecting
low concentrations of analytes.

3. **Wide Potential Range:** Mercury has a wide electrochemical potential range, allowing the DME
to work effectively across a broad spectrum of redox reactions. This makes it versatile for various
types of electrochemical studies.

4. **Minimized Interference:** The ability to renew the electrode surface frequently helps minimize
the effects of fouling and interference from reaction byproducts or surface contaminants.

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5. **Reproducibility:** The consistent and reproducible nature of the dropping process helps
achieve reliable and repeatable results in electrochemical measurements.

6. **Adaptability:** The DME can be used in both acidic and basic solutions, making it suitable for a
wide range of chemical environments.

Overall, the Dropping Mercury Electrode is valued in electrochemical analysis for its ability to
maintain a clean surface, high sensitivity, and versatility across different types of electrochemical
reactions.
Q.7 a) What are amperometric titrations? Draw common types of curves obtained in
amperometric titrations. Briefly discuss their experimental set up.
Ans: ### Amperometric Titrations

**Definition:**

Amperometric titrations are electrochemical techniques where the current response is measured as
a function of the added titrant. This method involves the continuous addition of a titrant to a
solution containing an analyte, and the change in current is monitored to determine the endpoint of
the titration.

**Common Types of Curves:**

1. **Typical Amperometric Titration Curve:**

The curve typically shows current (I) on the y-axis and the volume of titrant (V) added on the x-axis.
The key features of the curve include:

- **Initial Region:** At the start, the current is relatively stable.

- **Endpoint Region:** As the titrant is added, the current starts to change. The point where the
current change becomes significant is where the analyte is nearly completely reacted.

- **Final Region:** After the endpoint, the current stabilizes at a new value, reflecting the excess
titrant.

![Typical Amperometric Titration

Curve](https://upload.wikimedia.org/wikipedia/commons/5/56/Amperometric_titration.png)

*Image: Typical amperometric titration curve showing current response versus titrant volume.*

2. **Differential Amperometric Titration Curve:**

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A curve showing the differential change in current (dI/dV) versus the volume of titrant. The peak
corresponds to the titration endpoint, offering higher resolution for detecting the endpoint.

**Experimental Setup:**

1. **Electrochemical Cell:** Contains a working electrode, a counter electrode, and a reference

electrode. The working electrode is where the redox reactions occur.

2. **Titrant and Analyte Solutions:** The analyte is in the solution within the electrochemical cell,
and the titrant is added incrementally.

3. **Power Supply:** Provides a constant potential to the working electrode, allowing measurement
of the current.

4. **Current Measurement System:** Measures and records the current response as titrant is
added. This can be connected to a data acquisition system to plot the titration curve.

5. **Stirring Mechanism:** Ensures thorough mixing of the solutions to maintain uniformity.

Amperometric titrations are valuable for determining concentrations of

analytes and titrants with high precision and sensitivity, particularly useful
in analyzing electroactive species. b) List the factors
affecting TG curve. Taking a suitable example, explain the effect
of furnace atmosphere on TG curve.
ANS: Factors Affecting TG Curve

A Thermogravimetric (TG) curve, which plots the weight of a sample against temperature, is
influenced by several factors:

1. Heating Rate: The rate at which the temperature is increased affects the resolution
and shape of the TG curve. Faster heating rates can lead to broader peaks and less
detailed thermal events.
2. Sample Size and Shape: The amount and geometry of the sample can impact thermal
behavior. Larger samples may exhibit different thermal stability compared to smaller
ones due to variations in heat distribution.
3. Atmosphere: The composition of the atmosphere around the sample (e.g., air, inert
gas, reactive gas) can significantly affect the thermal decomposition and
oxidation/reduction reactions, altering the TG curve.

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4. Sample Composition: The presence of additives, impurities, or different phases (e.g.,

crystalline vs. amorphous) can influence thermal stability and decomposition
temperatures.
5. Heating Environment: Factors such as the type of furnace (e.g., electrically heated
vs. gas flow furnace) and the presence of any physical constraints can affect the
thermal analysis.
6. Baseline Drift: Instrumental factors such as drift in the baseline or noise can impact
the accuracy of the TG curve.

Effect of Furnace Atmosphere on TG Curve

Example: Decomposition of Calcium Carbonate (CaCO₃):

Calcium carbonate decomposes into calcium oxide (CaO) and carbon dioxide (CO₂) at
elevated temperatures. The reaction is:

Q.8 a) Draw a labeled diagram of the TG curve obtained by heating a mixture of 50 mg of calcium
oxalate monohydrate and 50 mg of barium oxalate monohydrate to 1200°C. Calculate the amount of
all mass losses. (

Q.8 a) Draw a labeled diagram of the TG curve obtained by heating a mixture of 50 mg of calcium
oxalate monohydrate and 50 mg of barium oxalate monohydrate to 1200°C. Calculate the amount
of all mass losses.
Ans:

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.
b) Explain the basic principle of Differential Scanning Calorimetry (DSC). Draw a
block diagram of DSC instrument
Ans: Principle of Differential Scanning Calorimetry (DSC)

Differential Scanning Calorimetry (DSC) is a thermal analysis technique used to measure the
heat flow associated with thermal transitions in a material. The basic principle of DSC
involves comparing the amount of heat required to increase the temperature of a sample and a
reference under controlled conditions.

Basic Principle:

1. Temperature Control:
o Both the sample and reference are subjected to a controlled temperature
program, typically involving heating, cooling, or holding at a constant
temperature. The sample and reference are maintained at nearly the same
temperature throughout the experiment.
2. Heat Flow Measurement:
o The key measurement in DSC is the differential heat flow between the sample
and the reference. When the sample undergoes a thermal event, such as
melting, crystallization, or a phase transition, it will absorb or release heat.
This causes a difference in heat flow between the sample and the reference,
which is detected by the DSC.
3. Endothermic and Exothermic Reactions:
o An endothermic reaction (e.g., melting) causes the sample to absorb heat,
resulting in a positive heat flow difference. Conversely, an exothermic

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reaction (e.g., crystallization) releases heat, resulting in a negative heat flow

difference.
4. DSC Curve:
o The DSC output is a plot of heat flow (y-axis) versus temperature (x-axis) or
time, called a DSC curve. Peaks on this curve indicate thermal transitions,
with the area under each peak corresponding to the enthalpy change of the
event.

Block Diagram of DSC Instrument:

Below is a simplified block diagram of a DSC instrument:

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Q.9 a) Describe various types of neutron sources available for NAA. Which one of these is most
suitable for trace element analysis?
Ans: **Neutron Sources for Neutron Activation Analysis (NAA)**

Neutron Activation Analysis (NAA) is a powerful technique for determining the concentrations of
elements in a sample by bombarding it with neutrons and measuring the resulting radioactive
isotopes. The effectiveness of NAA depends heavily on the neutron source used. The most
common neutron sources include:

### **1. Nuclear Reactors:**

- **Description:** Nuclear reactors are the most powerful neutron sources, providing a high flux
of thermal neutrons, typically in the range of \(10^{12} - 10^{14}\) neutrons per cm² per second.

- **Advantages:** The high neutron flux allows for the activation of even trace amounts of
elements, making reactors the most suitable for NAA, especially for trace element analysis.

- **Limitations:** However, they are expensive, require significant infrastructure, and are not
readily accessible.

### **2. Isotopic Neutron Sources:**

- **Description:** Isotopic sources, such as \(^{252}\text{Cf}\), emit neutrons spontaneously

through fission, producing a lower neutron flux compared to reactors.

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- **Advantages:** These sources are portable and relatively inexpensive, making them more
accessible for smaller laboratories.

- **Limitations:** The lower neutron flux limits their use to samples with higher concentrations
of elements.

### **3. Particle Accelerators:**

- **Description:** Accelerators generate neutrons by bombarding a target (e.g., beryllium) with

high-energy particles (e.g., protons or deuterons).

- **Advantages:** They provide a controlled and tunable neutron flux and can be used for
specific applications, such as generating fast neutrons.

- **Limitations:** The neutron flux is typically lower than that of nuclear reactors, and the setup
can be complex and costly.

### **4. Fusion Neutron Sources:**

- **Description:** Fusion-based sources generate neutrons through nuclear fusion reactions,

such as \( d(d,n)^3He \).

- **Advantages:** These sources can produce high-energy neutrons, useful for certain
specialized applications.

- **Limitations:** Fusion sources are still mostly experimental and not widely used for routine
NAA.

### **Most Suitable Source for Trace Element Analysis:**

- **Nuclear Reactors** are the most suitable neutron sources for trace element
analysis due to their high neutron flux, which allows for the detection of extremely low
concentrations of elements. The sensitivity and precision provided by reactor-based
NAA are unparalleled, making it the preferred choice for trace element analysis in
various fields, including environmental science, geology, and material science.
b) In what respects nuclear reactions are different from chemical reactions? Calculate Q
value of the reaction 63Cu = (n, γ)64Cu. Give that 63Cu = 62.929590, 64Cu = 63.929760,
n =1.008665 amu. Ans: Differences Between Nuclear Reactions and Chemical Reactions

Nuclear reactions and chemical reactions differ fundamentally in the following aspects:

1. Nature of the Reaction:

 Nuclear Reactions:
o Involve changes in the nucleus of an atom, leading to the transformation of
one element into another.
o Examples include fission, fusion, and radioactive decay.
 Chemical Reactions:

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o Involve changes in the electron configuration of atoms or molecules without

altering the nuclei.
o Examples include oxidation, reduction, and acid-base reactions.

2. Energy Involved:

 Nuclear Reactions:
o Involve the release or absorption of large amounts of energy, typically in the
range of millions of electron volts (MeV).
o The energy changes are due to the differences in nuclear binding energies.
 Chemical Reactions:
o Involve much smaller energy changes, usually in the range of a few electron
volts (eV).
o The energy changes result from the breaking and forming of chemical bonds.

3. Reaction Rates:

 Nuclear Reactions:
o Are not significantly influenced by factors like temperature, pressure, or
catalysts.
o The rate is governed by the intrinsic properties of the nuclei involved, such as
the half-life of radioactive isotopes.
 Chemical Reactions:
o Are heavily influenced by temperature, pressure, concentration, and the
presence of catalysts.
o The rate depends on the activation energy and the collisions between reacting
particles.

4. Conservation Laws:

 Nuclear Reactions:
o Must obey the conservation of mass-energy, charge, and nucleon number.
o The number of protons and neutrons may change, leading to the formation of
different elements or isotopes.
 Chemical Reactions:
o Must obey the conservation of mass, charge, and atoms.
o The identity of elements does not change, though atoms are rearranged into
different molecules.

5. Products:

 Nuclear Reactions:
o Produce new elements or isotopes, often accompanied by the emission of
radiation such as alpha, beta, or gamma rays.
 Chemical Reactions:
o Produce new chemical compounds but do not change the elemental identity of
the atoms involved.

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Q.10 a) Explain why (n, γ) reaction is most suited for NAA.

Ans: The \((n, \gamma)\) reaction, also known as neutron capture, is particularly well-suited for
Neutron Activation Analysis (NAA) due to several key factors that make it effective for qualitative and
quantitative analysis of trace elements.

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### **1. Broad Applicability:**

- The \((n, \gamma)\) reaction can occur in almost all elements, allowing for a wide range of
elements to be analyzed using NAA. When a nucleus captures a thermal neutron, it becomes an
excited isotope, which then decays by emitting gamma radiation. The energy and intensity of these
gamma rays are characteristic of specific elements, enabling their identification and quantification.

### **2. Sensitivity:**

- The \((n, \gamma)\) reaction is highly sensitive, making it possible to detect even trace amounts
of elements. This is particularly advantageous in fields like environmental science, geology, and
archaeology, where detecting low concentrations of elements is crucial.

### **3. Minimal Sample Preparation:**

- NAA using the \((n, \gamma)\) reaction requires little to no chemical treatment of the sample.
The sample can be analyzed in its original form, reducing the risk of contamination and loss of
material. This is a significant advantage over other analytical techniques that require extensive
sample preparation.

### **4. Non-Destructive Nature:**

- The \((n, \gamma)\) reaction is non-destructive, meaning the sample remains largely intact after
analysis. This is particularly important in cases where the sample is rare, valuable, or irreplaceable,
such as in the analysis of archaeological artifacts, forensic evidence, or rare minerals.

### **5. High Precision and Accuracy:**

- The \((n, \gamma)\) reaction provides high precision and accuracy in the measurement of
elemental concentrations. The gamma rays emitted are well-resolved, allowing for clear
differentiation between different elements and isotopes.

### **6. Wide Range of Elements:**

- Thermal neutrons, commonly used in the \((n, \gamma)\) reaction, have a high probability of
being captured by a wide variety of nuclei. This broadens the range of elements that can be
detected, including those that may be difficult to analyze using other methods.

### **Conclusion:**

The \((n, \gamma)\) reaction is ideally suited for NAA because it allows for the precise and
non-destructive analysis of a wide range of elements at trace levels with minimal sample
preparation. Its broad applicability and sensitivity make it a powerful tool in various scientific
fields.

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b) Discuss the principle of isotope dilution technique

Ans : The isotope dilution technique is an analytical method used to determine the
concentration of an element or compound in a sample by adding a known quantity of an
isotopically enriched form (tracer) of that element or compound. This technique is highly
accurate and is commonly used in various fields, including chemistry, biochemistry,
environmental science, and pharmacology.

Principle:

1. Addition of Isotopically Enriched Tracer:

o A known quantity of an isotopically enriched form of the element or
compound (the tracer) is added to the sample. This tracer is chemically
identical to the analyte but differs in isotopic composition. For example, if
measuring the concentration of a certain metal, an enriched isotope of that
metal is added.
2. Mixing and Equilibration:
o The sample and the tracer are thoroughly mixed to ensure that the isotopes are
evenly distributed throughout the sample. This allows the tracer to be
incorporated into the same chemical forms as the naturally occurring isotopes.
3. Measurement of Isotope Ratios:
o The isotopic composition of the element or compound in the sample is
measured using a mass spectrometer or another suitable analytical technique.
The ratio of the tracer isotope to the naturally occurring isotope(s) is
determined. Advantages:
o High Accuracy: The method compensates for potential losses of the analyte
during sample processing, as both the tracer and the analyte experience the
same conditions.
o Non-destructive: It allows for precise quantification without altering the
chemical composition of the sample.
o Applications:
o Isotope dilution is widely used in environmental analysis to measure trace
levels of pollutants, in pharmacokinetics to study drug metabolism, and in
geological dating to determine the age of rocks and minerals.

Advantages:

 High Accuracy: The method compensates for potential losses of the analyte during
sample processing, as both the tracer and the analyte experience the same conditions.
 Non-destructive: It allows for precise quantification without altering the chemical
composition of the sample.

Applications:

 Isotope dilution is widely used in environmental analysis to measure trace levels of

pollutants, in pharmacokinetics to study drug metabolism, and in geological dating to
determine the age of rocks and minerals.

o
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