book

Pharmaceutical Physical Chemistry: Theory and Practices

Name: Pharmaceutical Physical Chemistry: Theory and Practices
Author: S. K. Bhasin
ISBN: 9788131765272

by S. K. Bhasin

March 2012

Intermediate to advanced

608 pages

17h 39m

English

Pearson India

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Cover
Title Page
Contents
About the Author
Dedication
Preface
1. Behaviour of Gases
1.1 - Introduction1.2 - Gas Laws1.2.1 - Boyle’s Law1.2.2 - Charles Law1.2.3 - Avogadro’s Law1.2.4 - The Combined Gas Law Equation or the Gas Equation1.2.5 - Graham’s Law of Diffusion1.2.6 - Dalton’s Law of Partial Pressure1.3 - Kinetic Theory of Gases1.3.1 - Postulates (Assumptions) of Kinetic Theory1.4 - Derivation of Kinetic Gas Equation1.5 - Derivation of Gas Laws from Kinetic Equation1.5.1 - Some Useful Deductions from Kinetic Theory of Gases1.6 - Ideal and Real Gases1.6.1 - Ideal Gases1.6.2 - Real Gas1.7 - Deviations of Real Gases from Gas Laws1.7.1 - Deviations from Boyle’s Law1.8 - Causes of the Derivations from Ideal Behaviour1.9 - Van der Waals’ Equation (Reduced Equation of State) (Equation of State for Real Gases)1.9.1 - Units of van der Waals’ Constants1.9.2 - Significance of van der Waals’ Constant1.10 - Explanation of Behaviour of Real Gases on the Basis of van der Waals’ Equation1.11 - Isotherms of Carbon Dioxide—Critical Phenomenon1.12 - Principle of Continuity of States1.13 - Critical Constants1.13.1 - Relations Between van der Waals’ Constants and Critical Constants1.13.2 - Derivation of PcVc=3/8RTc from van der Waals’ Equation1.13.3 - Calculation of van der Waals’ Constants in terms of Tc and Pc1.14 - Law of Corresponding States1.14.1 - Significance of Law of Corresponding States1.15 - Limitations of van der Waals’ EquationRevision QuestionsMultiple Choice QuestionsAnswers
2. The Liquid State
2.1 - Introduction2.2 - General Characteristics of Liquids2.3 - Classification of Physical Properties of Liquids2.4 - Surface Tension2.4.1 - Some Important Results2.4.2 - Effect of Temperature on Surface Tension2.4.3 - Measurement of Surface Tension2.4.4 - Surface Tension in Everyday Life2.4.5 - Surface Tension and Chemical Constitution (Parachor)2.5 - Viscosity2.5.1 - Coefficient of Viscosity2.5.2 - Measurement of Viscosity2.5.3 - Effect of Temperature on Viscosity2.5.4 - Factors Affecting Viscosity2.5.5 - Viscosity and Chemical Constitution2.6 - Refractive Index2.6.1 - Measurement of Refractive Index2.6.2 - Refractive Index and Chemical Constitution2.7 - Optical Activity2.7.1 - Optical Activity2.7.2 - Specific Rotation2.7.3 - Optical Activity and Chemical Constitution2.8 - Polarity of Bonds2.8.1 - Polar Character of Covalent Bond2.9 - Dipole Moment2.9.1 - Unit of Dipole Moment2.9.2 - Dipole Moment and Molecular Structure2.9.3 - Application of Dipole MomentsRevision QuestionsMultiple Choice QuestionsAnswers
3. Solution
3.1 - Introduction3.2 - Modes of Expressing Concentration of Solutions3.3 - Raoult’s Law3.3.1 - For a Solution of Volatile Liquids3.3.2 - For a Solution of Non-volatile Solute3.4 - Ideal Solution3.4.1 - Non-ideal Solution3.4.2 - Solutions Showing Positive Deviations3.4.3 - Solutions Showing Negative Deviations3.4.4 - Factors Responsible for Deviations3.4.5 - Distinction Between Ideal and Non-ideal Solutions3.4.6 - Difference Between Solutions of Positive and Negative Deviations3.5 - Colligative Properties of Dilute Solution3.6 - Lowering of Vapour Pressure3.6.1 - Determination of Molecular Masses of Non-volatile Solute3.7 - Elevation in Boiling Point3.7.1 - Expression for the Elevation in Boiling Point3.7.2 - Calculation of Molecular Masses3.8 - Depression of Freezing Point3.8.1 - Expression for the Depression in Freezing Point3.8.2 - Calculation of Molecular Masses3.9 - Osmotic Pressure3.9.1 - Difference Between Osmosis and Diffusion3.9.2 - Osmotic Pressure3.9.3 - Determination of Osmotic Pressure Berkley and Hertley’s Method3.9.4 - Osmotic Pressure is a Colligative Property3.9.5 - Isotonic Solutions3.9.6 - Calculation of Molecular Masses from Osmotic Pressure3.10 - Abnormal Molecular Masses3.10.1 - Modified Equation for Colligative Properties in Case of Abnormal Molecular MassesRevision QuestionMultiple Choice QuestionsAnswers
4. Thermodynamics
4.1 - Introduction4.1.1 - Objective of Thermodynamics4.1.2 - Limitation of Thermodynamics4.2 - Some Common Thermodynamics Terms4.2.1 - Thermodynamic Equilibrium4.2.2 - Thermodynamic Processes4.2.3 - Reversible and Irreversible Processes4.2.4 - Thermodynamic Properties4.3 - Zeroth Law of Thermodynamics4.3.1 - Absolute Scale of Temperature4.4 - Work, Heat and Energy Changes4.4.1 - Work4.4.2 - Heat4.4.3 - Equivalence Between Mechanical Work and Heat4.4.4 - Internal Energy4.5 - First Law of Thermodynamics4.5.1 - Mathematical Formulation of First Law of Thermodynamics4.5.2 - Some Special Forms of First Law of Thermodynamics4.5.3 - Limitations of the First Law of Thermodynamics4.6 - The Heat Content or Enthalpy of a System4.7 - Heat Capacities at Constant Pressure and at Constant Volume4.7.1 - Heat Capacity at Constant Volume4.7.2 - Heat Capacity at Constant Pressure4.7.3 - Relationship Between Cp and Cv4.8 - Joule-Thomson Effect4.9 - Reversible-Isothermal Expansion of an Ideal Gas4.9.1 - Maximum Work4.10 - Second Law of Thermodynamics4.10.1 - Spontaneous Processes and Reactions (Basis of Second Law)4.10.2 - Spontaneous Reactions4.11 - Entropy4.11.1 - Mathematical Explanation of Entropy4.11.2 - Entropy Change in Chemical Reaction4.11.3 - Units of Entropy4.11.4 - Physical Significance of Entropy4.11.5 - Entropy Change Accompanying Change of Phase4.11.6 - Entropy Changes in Reversible Processes4.11.7 - Entropy Changes in Irreversible Processes4.11.8 - Entropy as Criterion of Spontaneity4.11.9 - Entropy Changes for an Ideal GasRevision QuestionsMultiple Choice QuestionsAnswers

5. Adsorption and Catalysis
5.1 - Adsorption5.2 - Types of Adsorption5.3 - Factors Affecting Adsorption of Gases on Solids5.4 - Adsorption Isobar (Effect of Temperature on Adsorption)5.5 - Adsorption Isotherm (Effect of Pressure)5.5.1 - Explanation of Type I Isotherm5.5.2 - Freundlich Adsorption Isotherm5.5.3 - The Langmuir Adsorption Isotherm5.5.4 - Verification5.5.5 - Explanation of Type II and III Isotherms5.5.6 - Explanation of Type IV and V Isotherms5.6 - Theory of Adsorption5.7 - Gibbs’ Adsorption Equation5.8 - Applications of Gibbs’ Adsorption Equation5.9 - Equation for Multi-Layer Adsorption (B.E.T. Equation)5.9.1 - Determination of Surface Area of the Adsorbent5.10 - Catalysis5.10.1 - Positive and Negative Catalyses5.11 - Homogeneous and Heterogeneous Catalyses5.12 - How Does a Catalyst Work?5.12.1 - Characteristics of Catalytic Reactions5.12.2 - Acid–Base Catalysis5.12.3 - Enzyme Catalysis5.13 - Mechanism of Homogeneous and Heterogeneous Catalyses5.13.1 - Significant Characteristics of Heterogeneous Catalysis5.13.2 - Facts Explained by Adsorption TheoryRevision QuestionsMultiple Choice QuestionsAnswers
6. Photochemistry
6.1 - Introduction6.2 - Thermochemical and Photochemical Reactions6.3 - Laws Governing Light Absorption — Lambert’s Law and Beer’s Law6.3.1 - Limitations of Lambert–Beer’s Law6.4 - Laws of Photochemistry6.4.1 - Grotthus–Drapper Principle of Photochemical Activation: (First Law of Photochemistry)6.4.2 - Stark–Einstein’s Law of Photochemical Equivalence— The Second Law of Photochemistry6.5 - Quantum Efficiency6.5.1 - Explanation of the Unexpected Behaviour6.5.2 - Classification of Photochemical Reactions (Based on their Quantum Efficiencies)6.6 - Study of Some Photochemical Reactions6.7 - Fluorescence and Phosphorescence6.7.1 - Fluorescence6.7.2 - Phosphorescence6.7.3 - Photophysical Process—Consequence of Light Absorption (Jablonski Diagram)6.7.4 - Mechanism of Fluorescence and Phosphorescence6.7.5 - Difference between Fluorescence and PhosphorescenceRevision QuestionsMultiple Choice QuestionsAnswers
7. Chemical Kinetics
7.1 - Introduction7.2 - Rate of a Reaction7.2.1 - Measurement of Rate of a Reaction7.2.2 - Expressing the Rate of a Reaction7.2.3 - Factors Influencing Rate of a Reaction7.3 - Rate Constant and Rate Equation7.3.1 - Differences Between Rate of a Reaction and Rate Constant7.4 - Order of a Reaction7.4.1 - Units for Rate Constant or Specific Reaction Rate7.5 - Molecularity of a Reaction7.5.1 - Differences Between Order and Molecularity of a Reaction7.6 - Zero-order Reactions7.6.1 - Characteristics of a Zero-order Reaction7.7 - Intergrated Rate Law Equation for First-order Reactions7.7.1 - Characteristics or Significance of First-order Reaction7.7.2 - Examples of the Reactions of First Order7.7.3 - Pseudo First-order Reaction7.8 - Second-order Reactions7.8.1 - Characteristics of Second-order Reaction7.8.2 - Example of the Second-order Reaction7.9 - Third-order Reaction7.9.1 - Characteristics of a Third-order Reaction7.9.2 - Example of Third-order Reactions7.10 - Reactions of Higher Order7.11 - Determination of Rate Law, Rate Constant and Order of Reaction7.12 - Some Complications in Determination of Order of a Reaction7.12.1 - Consecutive Reactions7.13 - Temperature Dependence of Reaction Rates7.13.1 - Explanation of Effect of Temperature7.13.2 - Arrhenius Equation7.14 - Mechanism of a Reaction (Concept of Molecularity and Order of a Reaction)7.15 - Theories of Reaction RatesRevision QuestionsMultiple Choice QuestionsAnswers
8. Quantum Mechanics
8.1 - Introduction8.2 - Classical Mechanics and Its Limitations8.2.1 - Limitations8.3 - Origin of Quantum Mechanics8.3.1 - Classical Mechanics Versus Quantum (or wave) Mechanics8.4 - Black Body Radiations8.5 - Kirchoff’s Law8.5.1 - Spectral Distribution of Black Body Radiation8.6 - Stefan-Boltzmann Fourth Power Law8.7 - Wien’s Displacement Law8.8 - Planck’s Radiation Law8.9 - Postulates of Quantum Mechanics8.10 - Operators in Quantum Mechanics8.10.1 - Types of Operators8.11 - Schrödinger Wave Equation8.11.1 - Derivation of Schrödinger Wave Equation8.12 - Eigenvalues and Eigenfunctions (or Wave Functions)8.12.1 - Physical Significance of the Wave Function8.13 - Normalized and Orthogonal Eigenfunctions8.14 - Concept of Atomic Orbital8.15 - Probability Distribution Curves8.16 - Radial Probability Distribution Curves8.16.1 - Radial Probability Distribution Curve for 1s Orbital8.16.2 - Radial Probability Distribution Curves for other s Orbitals8.16.3 - Comparison of Radial Probability, Distribution Curves for 1s with Other s Atomic Orbitals8.16.4 - Radial Probability Distribution Curves for p Orbitals8.16.5 - Comparison of Radial Probability Distribution Curves for 2s and 2p Orbitals8.16.6 - Comparison of Radial Probability Distribution Curves for 3s, 3p and 3d OrbitalsRevision QuestionsMultiple Choice QuestionsAnswers
9. Ionic Equilibria
9.1 - Introduction9.2 - Arrhenius Theory of Ionization9.2.1 - Degree of Dissociation or Ionization9.3 - Ionisation of Weak Electrolytes—Ostwald’s Dilution Law9.3.1 - Verification of Ostwald’s Dilution Law9.4 - Arrhenius Concept of Acids and Bases9.4.1 - Limitation of Arrhenius Theory9.5 - Ionisation Constant of Weak Acids and Bases (Arrhenius Concept)9.6 - Bronsted–Lowry Concept of Acids and Bases9.6.1 - Conjugate Acid Base Pairs9.6.2 - Relative Strength of Acids and Bases9.6.3 - Limitation of Bronsted—Lowry Theory9.7 - Lewis Concept of Acids and Bases9.7.1 - Limitations of Lewis Concept9.8 - Ionic Product of Water9.8.1 - Concentrations of H3O + and OH – ions in Aqueous Solutions of Acids and Bases9.9 - PH Scale9.9.1 - The POH Scale9.10 - Buffer Solution9.10.1 - Buffer Action of Buffer Solutions9.10.2 - Applications of Buffer SolutionsRevision QuestionsMultiple Choice QuestionsAnswers
10. Distribution Law
10.1 - Introduction10.2 - Conditions for the Validity of the Distribution Law10.3 - Effect of Temperature on Distribution Coefficient10.4 - Thermodynamic Derivation of Distribution Law10.4.1 - Principle10.5 - Distribution Law and Molecular State of Solute10.5.1 - Case I: When the Solute Undergoes Association in one of the Solvents10.5.2 - Case II: When the Solute Undergoes Dissociation in one of the Solvents10.5.3 - Case III: When the Solute Enters into Chemical Combination with One of the Solvents10.6 - Applications of Distribution Law10.6.1 - Determination of Solubility of a Solute in a Solvent10.6.2 - Determination of Molecular State of Solute in Different Solvents10.6.3 - Determination of Distribution Indicators10.6.4 - Study of Complex Ions10.6.5 - In the Process of Extraction10.6.6 - Application of Principle of Extraction To Desilverization of Lead10.6.7 - Determination of Degree of HydrolysisRevision QuestionsMultiple Choice QuestionsAnswers
11. Electrochemistry
11.1 - Introduction11.2 - Electrolysis11.2.1 - Faraday’s First Law of Electrolysis11.2.2 - Faraday’s Second Law of Electrolysis11.2.3 - Application of Electrolysis11.3 - Electrolytic Conduction11.3.1 - Differences Between Metallic Conductor and Electrolytic Conductor11.3.2 - Factors Affecting Electrolytic Conduction11.3.3 - Electrical Conductance11.3.4 - Specific Conductance11.3.5 - Equivalent Conductance and Molecular Conductance11.3.6 - Relation Between Specific Conductance and Equivalent Conductance11.3.7 - Experimental Measurement of Conductance11.3.8 - Effect of Dilution on Conductance11.4 - Kohlrausch Law11.4.1 - Applications of Kohlrausch’s Law11.5 - Migration of Ions11.5.1 - Migration Velocity of Ions and Change in Concentration—Hittorf Theoretical Device11.6 - Transport Number11.6.1 - Important Relations Concerning Transport Number11.6.2 - Factors Controlling Transport Number11.6.3 - Determination of Transport Numbers11.7 - Limitations of Arrhenius Theory11.8 - Modern Theory of Strong ElectrolytesRevision QuestionsMultiple Choice QuestionsAnswers
12. Electromotive Force and Oxidation–Reduction System
12.1 - Introduction12.2 - Single Electrode Potential12.2.1 - Definition12.3 - Standard Electrode Potential12.4 - Measurement of Single Electrode Potential12.4.1 - Sign Conventions12.5 - Reference Electrodes12.5.1 - Primary Reference Electrodes12.5.2 - Secondary Reference Electrodes12.5.3 - Advantages of Glass Electrode12.5.4 - Limitations of Glass Electrode12.6 - Electrochemical Series12.6.1 - Applications of Electrochemical Series12.7 - Cell Potential or EMF of a Cell12.7.1 - Calculation of EMF of a Cell12.8 - Derivation of Nernst Equation (Concentration Dependence of Electrode Potential)12.8.1 - Application of Nernst EquationRevision QuestionsMultiple Choice QuestionsAnswers
13. Solid State (Crystalline State)
13.1 - Introduction13.2 - Crystalline and Amorphous Solids13.3 - Some Terms Used in Crystal Structure13.4 - Crystal Lattice and Unit Cell13.5 - Elements of Symmetry13.5.1 - Plane of Symmetry and Reflections13.5.2 - Axis of Symmetry or Axis of Rotation13.5.3 - Centre of Symmetry or Inversion Centre13.5.4 - Improper Axis or Rotation Reflector Axis and Improper Rotation13.5.5 - Axis of Rotation Inversion13.5.6 - Total Elements of Symmetry13.6 - Crystallographic Designations13.6.1 - Weiss Indices (Parameter System of Weiss)13.6.2 - Index System of Miller (Miller Indices)13.7 - Laws of Crystallography13.7.1 - The Law of Constancy of Interfacial Angles13.7.2 - The Law of Rationality of Indices13.7.3 - The Law of Symmetry13.8 - Crystal Systems13.9 - Types of Unit Cells in Crystal System (Bravais Lattice)13.10 - Bragg’s Method of Crystal Analysis13.10.1 - Principle13.10.2 - Derivation of Bragg’s Equation13.10.3 - Bragg’s Method for Determining Crystal Structure13.10.4 - Applications of Bragg’s Equation13.11 - Types of Crystalline Solids13.11.1 - Ionic Solids13.11.2 - Metallic Solids13.11.3 - Covalent Solids13.11.4 - Molecular SolidsRevision QuestionsMultiple Choice QuestionsAnswers
14. Chemical Bonding
14.1 - Introduction14.2 - Valence Bond (Vb) Theory14.3 - Molecular Orbital (Mo) Theory14.3.1 - Molecular Orbitals14.3.2 - Conditions for Atomic Orbitals to Form Molecular Orbitals14.3.3 - Difference Between Atomic and Molecular Orbitals14.3.4 - Formation of Bonding and Anti-bonding Molecular Orbitals (Lcao Method)14.3.5 - Bonding and Anti-bonding Molecular Orbitals in Terms of Wave Functions14.3.6 - Characteristics of Bonding and Anti-bonding Molecular Orbitals14.3.7 - Combination of Atomic Orbitals—Sigma (s) and Pi (p) Molecular Orbitals14.4 - Relative Energies of Molecular Orbitals and Filling of Electrons14.5 - Stability of Molecules14.5.1 - Stability of Molecules in Terms of Bonding and Anti-bonding Electrons14.5.2 - Stability of Molecules in Terms of Bond Order14.6 - Molecular Orbital Configurations14.6.1 - Bonding in Some Homonuclear Diatomic Molecules and Ions – Electronic Configurations14.6.2 - Helium Ion, He2+14.6.3 - Nitrogen Molecule, N214.6.4 - Oxygen Molecule, O214.6.5 - The Fluorine Molecule, F214.6.6 - Hypothetical Neon Molecule, Ne214.6.7 - Molecular Orbital Electronic Configuration of Some Common Heteronuclear Molecules14.7 - Comparison of Valence Bond (Vb) Theory and Molecular Orbital (Mo) Theory14.7.1 - Points of Similarly14.7.2 - Points of DifferenceRevision QuestionsMultiple Choice QuestionsAnswers
15. Phase Equilibria
15.1 - Introduction15.2 - Explanation of the Terms Involved15.2.1 - True and Metastable Equilibrium15.2.2 - Phase15.2.3 - Components15.2.4 - Degrees of Freedom or Variance15.3 - Mathematical Statement of Phase Rule15.4 - Phase Diagrams15.5 - One-component Systems15.6 - The Water System15.7 - Sulphur System15.8 - Application of Phase Rule To Two-component Systems (Liquid–Solid Phase Diagram)15.9 - Type A—Simple Eutectic System15.9.1 - Characteristics of Eutectic Point15.9.2 - Use of Eutectic Systems15.9.3 - Lead–Silver System15.9.4 - Pattinson’s Process for Desilverization of Lead15.10 - Type B—System in Which Two Components form a Stable Compound (Zinc–Magnesium Alloy System)15.10.1 - Eutectic Points and Congruent Melting Point15.11 - Type C—The Two-component Form: A Compound With Incongruent Melting Point15.11.1 - Sodium – Potassium System15.12 - Thermal Analysis (Cooling Curve)Revision QuestionsMultiple Choice QuestionsAnswers
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Overview

Physical chemistry is a compulsory paper offered to all the students of pharmacy. There is a dearth of good books that exclusively cover the syllabi of physical chemistry offered to pharmacy courses. Pharmaceutical Physical Chemistry: Theory and Practices has been designed considering their requirements laid down by AICTE and other premier institutes/universities. Apart from the theory 20 most common laboratory experiments have been included to make this book a unique offering to the students of pharmacy.

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