Physical Pharmacy and Instrumental Methods of Analysis, 1st ed. 2023

1. Introduction and Physical Properties of Drug Molecules
1.1 Introduction
1.2 Dimensions and Units
1.3 Electromagnetic Radiation
1.4 Atomic Spectra
1.5 Molecular Spectra
1.6 Ultraviolet and Visible Spectrophotometry
1.7 Fluorescence and Phosphorescence
1.8 Infrared Spectroscopy
2. Solution
2.1 Definition
2.2 Solvent in a Solution
2.3 Types of solutions
2.4 Methods of Expressing the Concentration of a Solution
2.5 Factors Affecting Solubility
2.5.1 Effect of Temperature
2.5.2. Nature of Solute and Solvent
2.5.2 Effect of Pressure
2.6 Solubility Expressions
Judge Yourself
3. Colligative Properties
3.1 Introduction
3.2 Definition
3.3 Classification
3.3.1 Lowering of Vapour Pressure
3.3.2 Measurement of Lowering of Vapor Pressure
3.4 Osmotic Pressure
3.4.1 Theories of Semi-Permeable Membrane
Contents

3.4.2 Osmotic Pressure
3.4.3 Measurement of Osmotic Pressure
3.4.4 Effects of Osmosis
3.4.5 Reverse Osmosis and Desalination
3.5 Elevation of Boiling Point
3.5.1 Determination of Boiling Point Elevation
3.6 Depression of Freezing Point
3.6.1 Determination of Molar Mass from Depression in
Freezing Point
3.6.2 Determination of Depression in Freezing Point
Judge Yourself
4. The Distribution Law
4.1 Introduction
4.2 Definition
4.3 Solubilities and Distribution Law
4.4 Limitations of Distribution Law
4.5 Thermodynamic Derivation
4.6 Modifications in Distrabution Law
4.6.1 When Solute Undergoes Association in
any one of the Solvent
4.6.2 When Solute Undergoes Dissociation in
any one of the Solvent
4.6.3 The Solute Enters into Chemical Combination
with one of Solvent
4.7 Applications of Distribution Coefficient
4.7.1 Association of a Solute
4.7.2 Dissociation of a Solute
4.7.3 Distribution Indicators
4.7.4 Extraction with a Solvent
4.7.5 Partition Chromatography
Judge Yourself
5. Ionization and Ionic Equilibria
5.1 Introduction
5.2 Arrhenious Concept [Savanti Arrhenius (Doctoral thesis in 1887)]
5.2.1 Role of Water
5.3 Bronsted–Lowery Concept
5.4 Lewis Electronic Concept

5.4.1 Hydrogen Ion Concentration
5.4.2 Ionization of Water
5.5 Ionization of Acids and Bases
5.5.1 Conversion of Hydrogen Ion Concentration to pH.
5.5.2 Common Ion Effect
5.6 Buffers
5.6.1 Buffer of Weak Acid and its Salt
5.6.2 Buffer of Weak base and its Salt: NH4OH & NH4Cl
5.6.3 Buffer Capacity
5.6.4 Maximum Buffer Capacity
5.6.5 Buffer Capacity and Neutralization Curve
5.7 Hydrolysis of Salt
5.7.1 Hydrolysis Constant
5.7.2 Degree of Hydrolysis
5.7.3 Salt of Weak Base and Strong Acid
5.7.4 Salt of Weak Acid and Weak Base
5.8 Solubility Product
Judge Yourself
6. Chemical Kinetics
6.1 Introduction
6.2 Rate and Order of Reaction
6.3 Molecularity
6.4 Specific Rate Constant
6.5 Units of Basic Rate Constant
6.6 Calculation of Reaction Rate
6.7 Zero Order Reaction
6.7.1 Characteristics of Zero Order Reaction
6.7.2 Example of Zero Order Reaction
6.7.3 Apparent Zero Order Kinetics
6.8 First Order Reaction
6.8.1 Examples of Order Rate Kinetics
6.9 Second Order Reaction
6.10 Methods for Determination of Order of A Reaction
6.10.1 Method of Integration (Hit and trial method)
6.10.2 Graphical method
6.10.3 Half Life Method
x Physical Pharmacy and Instrumental Methods of Analysis
6.11 Factors that Affect Reaction Rate
6.11.1 Concentration
6.11.2 Pressure
6.11.3 Surface Area
6.11.4 Nature of Reactants
6.11.5 Temperature
6.12 Theories of Chemical Kinetics
6.12.1 Collision Theory
6.12.2 Transition State Theory
6.13 Decomposition and Stabilization of Medicinal Agents 95
6.14 Summary
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7. Catalysis
7.1 Introduction
7.2 Types of Catalyst
7.2.1 Catalyst Poison
7.2.2 Induced Catalysis
7.2.3 Catalyst Promoter
7.2.4 Autocatalysis
7.3 Characteristics of a Catalyst
7.4 Theories of Catalysis
7.4.1 The Intermediate Compound Formation Theory
7.4.2 The Adsorption Theory
7.5 Types of Catalysis
7.5.1 Homogenous Catalysis
7.5.2 Heterogeneous Catalysis
7.5.3 Enzyme Catalysis
7.6 Catalytic Poisoning
7.7 Applications of Catalysis
Judge Yourself
8. Electrochemistry
8.1 Introduction
8.2 Definition of Terms
8.2.1 Conductance (c)
8.2.2 Resistance
8.2.3 Conductivity
Contents xi
8.2.4 Resistivity
8.2.5 Molar Conductance
8.2.6 Equivalent Conductance
8.3 Types of Conductors
8.4 Laws of Electric Current
8.4.1 Ohms Law
8.4.2 Faraday`s Law of Electrolysis
8.4.3 Kohlrausch’s Law
8.4.4 Electrolytic Conductance
8.4.5 Mechanism of Electrolytic Conductance
8.6 Conductivity Cell
8.6.1 Types of Conductivity Cell
8.6.2 Cell Constant
8.7 Factors Affecting Electrolytic Conductance
8.7.1 Nature of Electrolyte
8.7.2 Concentration of the Solution
8.7.3 Temperature
8.8 Applications
8.8.1 Determination of Degree of Dissociation of
Weak Electrolyte
8.8.2 Basicity of Organic Acids
8.8.3 Determination of Solubility and Solubility
Product of Sparingly Soluble Salt
8.8.4 Ionic Product of Water
8.8.5 Determination of Total Dissolved Solids (TDS) in Water
Judge Yourself
9. Potentiometry
9.1 Introduction
9.2 Cell
9.2.1 Galvanic Cell
9.2.2 Notation
9.2.3 Conductance in Cell
9.2.4 Liquid Junction
9.3 Cell Types
9.3.1 Concentration Cell
9.3.2 Electrolytic Cell
9.3.3 Electrochemical Cell
xii Physical Pharmacy and Instrumental Methods of Analysis
9.4 Reversible and Irreversible Cells
9.5 Electrode Potential
9.5.1 Calomel Electrode
9.5.2 Standard Electrode Potential
9.6 Cell Potential
9.7 Reversible Electrodes
9.7.1 Electrodes Reversible with Respect to
Cation or Electrode of First Kind
9.7.2 Electrodes Reversible with Respect to
Anion or Electrode of Second Kind
9.7.3 Electrodes of Third Kind
9.7.4 Oxidation Reduction Electrodes or
Electrodes of Fourth Kind 134
9.8 Some Common Reversible Electrodes
9.8.1 Meta-Metal Ion Electrode
9.8.2 Gas Electrode
9.8.3 Ion Selective Electrodes (ISE)
9.8.4 Selectivity of Ion Selective Electrodes
9.9 Sensing Electrodes
9.9.1 Polymer Membrane Electrodes (Organic Ion
Exchangers and Chelating Agents)
9.9.2 Solid State Electrodes (Insoluble Conductive
Inorganic Salts)
9.9.3 Gas Sensing Electrodes
9.9.4 Glass Membrane Electrodes
9.10 Glass Electrode
9.10.1 Construction
9.10.2 Storage
9.10.3 Advantages
9.10.4 Disadvantage
9.11 Reference Electrodes
9.11.1 Primary Reference Electrode e.g.
Standard Hydrogen Electrode (SHE)
9.11.2 Working 142
9.11.3 Secondary Reference Electrode
9.11.4 Silver/Silver Chloride Electrode
9.12 Potentiometric Titration
9.12.1 Modes of Titration
Contents xiii
9.12.2 Acid Base Titration
9.12.3 Oxidation Reduction Titration
9.12.4 Complexometric Titration
9.13 Summary
Judge Yourself
10. Aquametry
10.1 Introduction
10.2 Chemical Methods
10.2.1 The Karl Fischer Titration Method
10.2.2 Direct Titration by Karl Fischer Reagent
10.2.3 Residual Titration using Karl Fischer Reagent
10.2.4 Coulometric Method: (Electrometric Method)
10.3 Physical Methods (Azeotropic Distillation)
10.3.1 Apparatus
10.3.2 Procedure
10.4 Gas Chromatographic Method
10.5 Conductometric Method Of Water Determination
10.6 Thermal Method
10.6.1 Loss on Drying
10.7 Summary
Judge Yourself
11. Spectrofluorimetry
11.1 Introduction
11.2 Theory
11.3 Rate of Absorption And Emission
11.4 Deactivating Factors
11.4.1 Vibrational Relaxation
11.4.2 Internal Conversion
11.4.3 External Conversion
11.4.4 Intersystem Crossing
11.5 Factor Which Effect Fluorescence and Phosphorescence
11.5.1 Transition Type in Fluorescence
11.5.2 Quantum Yield or Efficiency
11.5.3 Structure
11.5.4 Structure Rigidity
11.5.5 Temperature and Solvent Effect
xiv Physical Pharmacy and Instrumental Methods of Analysis
11.5.6 Effect of Dissolved Oxygen
11.5.7 Concentration
11.6 Instrumentation
11.6.1 Light Source
11.6.2 Monochromator
11.6.3 Detectors
11.7 Wavelength Correction and Spectra Correction
11.8 Sample Handling
11.9 Applications
11.9.1 Direct Method
11.9.2 Indirectly by Decrease
11.10 Types of Fluorescence Assay
11.10.1 The Formation of Chemical Derivatives
11.10.2 Fluorescence Quenching Analysis
11.10.3 Kinetic Methods of Analysis
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12. Polarimetry
12.1 Introduction
12.2 Principle
12.3 Optical Rotation and Type of Molecules Analyzed
12.4 Factors Affecting Angle of Rotation
12.5 Specific Rotation
12.6 Molecular Rotation
12.7 Intrinsic rotation
12.8 Temperature
12.9 Instrumentation
12.10 Application
Judge Yourself
13. Refractometry
13.1 Introduction
13.2 Refractometry
13.2 Laws of Refraction
13.4 Critical Angle of Refraction
13.5 Polarizability and Refractive Index
13.6 Refractive Index and Temperature
Contents xv
13.7 Measurement of refractive Index
13.7.1 Abbe’s Refractometers
13.9 Application
13.10 Summary
Judge Yourself
14. Chromatography Techniques
14.1 Introduction
14.2 Classification of Chromatogaphic Technologies
14.2.1 On the basis of Property used to Separate
14.2.2 On the basis of Stationary Phase
14.2.3 On the basis of Solvent Phase
14.2.4 On the basis of Elution (development) Method
14.3 Theory of Chromatography
14.3.1 Plate Theory
14.3.2 Rate Theory
14.4 Thin-layer Chromatography (TLC)
14.4.1 Principle of TLC
14.4.2 Advantages of TLC
14.4.3 Procedure
14.4.4 Adsorbents
14.4.5 Preparation of Chromatoplates
14.4.6 Activation of Plates
14.4.7 Solvent System
14.4.8 Application of sample
14.4.9 Development of Chromatograms
14.4.10 Location of Spots
14.4.11 Evaluation of the Chromatogram
14.4.12 Applications
14.5 Paper Chromatography
14.5.1 Principle
14.5.2 Procedure
14.5.3 Types of Paper Chromatography
14.5.4 Applications
14.6 Column Chromatography
14.6.1 Experimental Aspects of Column Chromatography
14.6.2 Column Characteristics
xvi Physical Pharmacy and Instrumental Methods of Analysis
14.6.3 Development/Elution Technique
14.6.4 Detection of Compounds
14.6.5 Factors affecting Column Efficiency
14.6.6 Application
14.7 Gas Chromatography
14.7.1 Types of Gas Chromatography
14.7.2 Experimental Aspects of Chromatography
14.7.3 Procedure
14.7.4 Derivitisation of Sample
14.7.5 Pretreatment of Solid Support
14.7.6 Various Factors Affecting Separation Process
14.7.7 Parameters used in GC
14.7.8 Applications of Gas Chromatography
Judge yourself