Pharmaceutical Analysis-III
 (Instrumental Methods) SPECTROANALYTICAL & ELECTROANALYTICAL TECHNIQUES
  by P.C. Kamboj
 
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   ISBN 978-81-85731-68-1; 1st Ed. 2011; pp.xvi+552

   Delhi price: 290      Outside Delhi price: 305      Overseas price : 870

 About The Book  


   This book contains SpectroAnalytical and ElectroAnalytical Techniques in ample details to serve the purpose of pharmacy and general (U.G. and P.G.) chemistry courses. .

This volume includes 17 chapters describes Spectro- and Electro Analytical techniques. The first chapter describes the various terms used in spectroscopy in detail and ten chapters provide a vivid description of different types of spectroscopy including UV, IR, Visible, Fluorescence, Phosphor-escence, Nephelometry / Turbid-imetry, NMR, ESR, FEAS, AAS and mass spectrometry etc. The last 6 chapters include the introductory terms and basic definitions related to electrochemistry; the techniques of potentiometry, conductometry, voltametery (polarography), amperometry and coulometry. Some practical exercises have been added; a detailed contents, index and 15 appendices included.

 Content


SpectroAnalytical Techniques

1 SpectroAnalytical Methods-Intro. and General Features
Introduction
What is spectroscopy; Spectroanalytical techniques classified, Nature of Radiant Energy
Electromagnetic Radiation
Wave properties, Wave parameters and units, amplitude, wavelength, frequency, wavenumber, time period, wavefront, velocity, power and intensity
Quantization of Energy
Numerical problems
Electromagnetic Spectrum
Radiofrequency region, Microwave region, Infrared region, Visible and uv regions, X-ray region, Gamma ray region
Interaction of Radiant Energy with Matter
Some Phenomena Related with Wave Nature of Electromagnetic Radiation; Mathematical expression of a wave, Superposition of waves, Diffraction of waves, Coherency of Radiation, Transmission of radiation, Reflection and refraction of light, Scattering of radiation, Rayleigh scattering, Tyndall effect, Raman Scattering, Polarization of radiation
Phenomena Based on Energy of Electromagnetic Radiation
Atomic spectra and atomic energy levels, Effects of various regions of electromagnetic radiation upon matter, Molecular energy, translational energy, electronic energy, vibrational energy, rotational energy, Depiction of energy levels
Interaction of Various Regions of Electromagnetic Radiation with Molecules
Radiofrequency region, Microwave region, Infrared region, Visible and ultraviolet region, Raman scattering, Gamma ray region
Decay of Electronically Excited States (Molecular Luminescence or Emission)
Nonradiative dissipation of energy, Electron spin, singlet/triplet excited states, Theory of fluorescence and phosphorescence, energy-level diagrams for photoluminescent molecules, deactivation processes, vibrational relaxation and internal conversion processes, external conversion, intersystem crossing, phosphorescence
Absorption of Electromagnetic Radiation (Quantitative Aspects), Beer's Law
Alternative derivation
Measurement of Absorbance and Transmittance
Single beam photometer
Composition of Mixtures of Absorbing Species (Method of Simultaneous Equations)
Using Beer's Law
Absorbance and transmittance spectra
Deviations from Beer's Law
Real deviations, Relationship between absorbance and concentration, Instrumental deviations, Presence of stray radiation, Instrumental noise and transmittance, Chemical deviations
Resolving Power
Signal-to-Noise Ratio
Width of Spectral Lines
Doppler broadening, Collision broadening, Quantum mechanical broadening
Complexity of Spectra and Intensity of Spectral Lines
Measurement of a Spectrum
Absorption spectrometer
Enhancement of Spectra (Computer Averaging Technique, CAT)
Fourier-Transform Spectroscopy
Lasers
Practical Lasers
Ruby crystal laser, Nd laser, Gas lasers, CO2 laser, Dye lasers, Semiconductor diode lasers
Solved Numerical Problems
Questions,

2 Ultraviolet/Visible Molecular Absorption Spectrometry Introduction
Vacuum UV region, Simple UV region, Visible region
Electronic Transitions and Origin of Spectra
Organic Chromophores
Visibility of Human Eye
Some Terms and Different Shifts in UV-Visible Spectroscopy
Molecules Containing More than One Chromophore and/or Auxochromes
Applications to Nonabsorbing Species
Solvents Used in UV-Visible Absorption Spectrometry
Effect of Solvent, pH, and Temperature Upon UV-Spectra of an Organic Compound
Solvent effect, pH effect, Temperature effect
d-d Transitions,
Charge-Transfer Transitions
Photometric and Spectrophotometric Titrations
Instrumentation, Process of titration, Applications, Advantages
Radiant Energy Sources
Tungsten/halogen lamps, H2 or D2 discharge lamps, Xenon arc lamp
Monochromators (or Wavelength Selectors)
Filters, Interference wedges, Prisms, Diffraction gratings, concave gratings, Holographic gratings, Echelle grating
Sample Cells / Cuvettes
Radiation Transducers (or Detectors)
Photovoltaic cells (Barrier-layer cells), Photoelectric cells (or vacuum phototubes), Photomultiplier tubes, Photodiode arrays
Instrumentation (Optical Instruments and their Types)
Colorimeters, Photometer, Spectroscope, Spectrometer, Spectrograph, Spectrophotometer
Single-Beam Instruments
Double-Beam Instruments
Comparism between Colorimetry and Fluorimetry
Chemical and Pharmaceutical Applications
Identification of compounds and functional groups, Woodward rules, Cis-trans geometrical isomers, Preference over two tantomeric forms, Determination of concentration of an unknown solution, Structural analysis, vitamin A1 and A2, cis-trans isomerism and steric effects, conjugated systems in keto-steroids, Detection of impurities, Study of chemical reactions, charge-transfer complexes
Questions

3 Molecular Luminescence Spectroscopy
Introduction
Spectrofluorometry
Factors that Affect the Fluorescence and Phosphorescence
Quantum yield, Types of transitions in fluorescence, Structural factors, Effect of structural rigidity, Temperature and solvent effects, Effect of pH on fluorescence, Dissolved oxygen
Relationship between Concentration and Fluorescence/Phosphorescence Intensity
Factors Affecting Intensity of Fluorescence
Concentration, Quantum efficiency, Intensity of incident radiation beam, Pathlength, Adsorption, Photodecomposition, Quenching, collisional impurity quenching, energy transfer quenching, concentration quenching, inner-filter effect
Emission and Excitation Spectra
Instrumentation for Fluorescence
Sample cell geometry, Spectral slit-widths
Components of Fluorometers and Spectrofluorometers
Sources, Filters and monochromators, Transducers (detectors), Cells and its compartment
Single-Beam Fluorometers, Spectrofluorometers
Double-Beam spectrofluorometers
Advantages of Fluorimetry
High sensitivity, Selectivity
Applications of Fluorerscence in General and Pharmaceutical Analysis
Fluorescent Indicators
Some Important Determinations
D of rivoflavin (vitamin B2), D of thiamine hydrochloride (vitamin B1), D. of quinine in tonic water, D. of codeine and morphine in a mixture, D. of tetracycline in serum, (Read D. = determination)
Questions

4 Colorimetry
Introduction
General Considerations
Visual and photoelectric colorimetry
Specificity of the colour reaction, Beer's law obeyance, Stability of the colour, Reproducibility, Clarity of solution, High sensitivity, Derivatization
Methods for Colour Measurements (Visual Comparison)
Standard series method, Dilution method, Duplication method (colorimetric titration), Matching method
Photoelectric Colorimetry (or, Absorptiometry)
Colorimetric Determinations
D of iron (Duboscq colorimeter), D. of max for KMnO4 and verification of Beer's law; also D. of unknown concentration, D. of iron (spectrophotometrically), D. of pKa of an acid-base indicator, D. of composition of a complex
Applications to Drugs

5. Nephelometry and Turbidimetry
Introduction
Choice between Turbidimetry and Nephelometry
Principles of Turbidimetry and Nephelometry
Instrumentation for the Techniques
Visual (or comparator type) nephelometers, standards, EEL nephelometer
Nepheloturbidimeter
Du Pont model -430 Turbidimeter
Applications of Turbidimetry and Nephelometry
Turbidimetric Titrations
Some Important Determinations
D. of SO42–, D. of PO43–
Biochemical Analyses

6 Infrared Spectroscopy
Introduction
Stretching Vibrations in a Diatomic Molecule
Anharmonic Oscillator (Overtone Transitions)
Vibrations of Polyatomic Molecules
Types of Molecular Vibrations
Stretching vibrations, symmetric and asymmetric, Bending (deformation) vibrations, rocking, scissoring, wagging, twisting, Examples, linear triatomic molecules, bent triatomic molecules, ethylene molecule, benzene
Infrared Sources
Nernst glower, Globar sources, Incandescent wire sources, Mercury arc, Tungsten filament lamp, Carbon dioxide laser source
Infrared Detectors (or Transducers)
Thermocouple, Bolometers, and thermistors, Golay pneumatic detector, pyroelectric detectors, Photon detectors
Sample Handling in Infrared
Gaseous samples, Liquids and solutions, Solid samples
Monochromators
Infrared Instruments
Structural Analysis
Qualitative analysis, Group frequencies
Some IR Absorption Spectra
Quantitative Analysis
Measuring IR absorption bands, Using Beer;s law, determination of concentration, use of a calibration graph, standard addition method
Applications of Infrared Spectroscopy
Structure elucidation, Determination of purity, Detection of moisture/hydrogen bond, Detection of the shape / symmetry of a molecule, Study of chemical reactions, Tautomerism, Coordination compounds, Miscellaneous uses

7 Nuclear Magnetic Resonance (NMR) Spectroscopy
Introduction
Theory of NMR in Quantum Mechanical Terms
Larmor precession
Relaxation Processes
Structural Information NMR Spectra, Instrumentation and Measurement
Sample Preparation
Reference Standard
Chemical Shift Shielding and De-shielding of Protons
Spin-Spin Interactions (or, Coupling)
(Fine structures in NMR)
Proton NMR spectrum of Ethanol
Applications of NMR Spectroscopy

8 Electron Spin Resonance (ESR) Spectroscopy
Introduction
Splitting of Electron Energy Levels by a Magnetic Field
Instrumentation of ESR
ESR Spectra
Width of Spectral Lines
Hyperfine Structures (Electron-Nucleus Coupling)











 
9. Atomic Flame Emission Spectroscopy (Flame Photometry)
Introduction
Principles of Flame Photometry
Instrumentation for Atomic Emission Spectrometry
Methods for introducing the sample into the flame, nebulization, hydride generation technique, aspiration of solid samples, direct sample insertion, Atomization by a flame, flames, burners (as flame atomizers), Optical system, Photodetectors, Recorders/readout meters
Sample Preparation
Flame Photometers
Single-beam, Double-beam
Flame Emission Spectrometry
Optimization of Flame Processes
Interferences in Flame Photometry
Spectral interference, Background corrections, Ionization interference, Self-absorption, Physical interference
Experimental Procedure for Quantitative Analysis
Calibration curve procedure, Standard addition procedure, Internal standard procedure
Applications of Flame Emission Spectroscopy
Determinations by Flame Emission spectrometry

10 Atomic Flame Absorption Spectroscopy [AAS]
Introduction
Principles of Atomic Absorption Spectroscopy
Linewidth Effects and Absorption Characteristics
Atomic Absorption Instrumentation
Hollow cathode lamps, Electrodeless discharge lamps, Modultion of the source, Sample vaporization, flame vapourization, flameless vapourization, graphite tube furnace, carbon rod or filament, Vapourization by reduction (generation of a hydride)
Spectrophotometers for AAS
Single beam, 309; Double beam
Applications of Atomic Absorption Spectrometry
Relative Detection Limits of AAS and FES
Experimental Section
Determination of Ca2+ by AAS
Determination of Ca2+ by AAS in an unknown solution
Determination of Na+ by FES
Determination of Na+, K+ and Ca2+ (in mineral waters) by FES

11 Mass Spectrometry
Introduction
Design and Sample Flow in a Mass Spectrometer
Molecular Mass Spectra (Cleavage Reactions and Molecular Ion)
Sample Size and its Placement
Vacuum Creation
Sample Inlet Systems
Ion Sources (Ionization Chamber)
Electron impact ionization sources, Chemical ionization sources, Field ionization
Mass Analysers
Single focussing magnetic sector analysers, Double focussing mass spectrometers, Qudrupole mass spectrometers, Time-of flight mass analysers, Fourier-transform-ion cyclotron resonance analyser
Detection and Recording
Resolution
Fragmentation Process
Identification by Fragmentation
Determination of Molecular Formulae
Molecular Ion
Atomic Weights in Mass spectrometry
Determination of Natural Abundance of the Isotopes
Example
Representation of Some Simple Mass Spectra
Metastable Ions
Applications of Molecular Mass Spectrometry
Advantages of the Mass spectrometry

ElectroAnalytical Techniques

12 Introduction to Electrochemistry
Introduction
Oxidation and Reduction Reactions
Oxidation State (or Number)
Galvanic Cells and Half-Reaction Concept
Liquid Junction Potential and its Elimination
Single Electrode Potential (Double Layer Concept)
Balancing Redox Reactions
Electrode Potential and Standard Electrode Potential
More About Sign Conventions
Effect of Concentration on Electrode Potentials (Nernst's Equation)
Formal Potentials
Redox Indicators
Principles Involved in Redox Titrations
Equilibrium constant and feasibility of redox reactions, Representation of a titration curve for a redox system, Some oxidants as titrants
Electrochemical Cells with Significant Currents
Ohmic potential (IR drop), Polarization, Overvoltage (activation overpotential), Concentration overvoltage or concentration polarization

13 Potentiometric Measurements
Introduction
Principles of the Potentiometry
Accuracy in Potentiometric Methods
Advantages of the Potentiometric Methods
Reversible Electrodes
Electrodes of the first type (or electrodes reversible with respect to cations), metal-metal ion electrodes, amalgam electrodes, gas electrodes, Electrodes of the second type (or electrodes reversible with respect to anions, calomel electrode, silver-silver chloride electrode, gas electrode, Electrodes of the third type, Electrodes of the fourth type (or Redox electrodes)
Standard (or Normal) Hydrogen Electrode (SHE or NHE)
Hildebrand bell-type, Lindsey type, advantages, disadvantages
Calomel Electrode
Silver-Silver Chloride Electrode
Indicater Electrodes
Metal-metal ion electrode, electrodes of the first type, electrodes of the second type, electrodes of the third type, inert (or redox) metal electrodes, Membrane electrodes, glass electrode, merits, demerits, precautions in use
Measurement of the Cell EMF with a Potentiometer
Principle of potentiometer, Standard (Weston) cell, Potentiometers
Potentiometric Measurement of pH and pH Meter
With hydrogen electrode, 402; using Quinhydrone electrode, 403; Glass-membrane electrode, 405; Antimony-antimony oxide electrode
Operational Definition of pH
Measurement of pH with a pH Meter
Potentiometric Titrations
Principal Types of Potentiometric Titrations
Acid-base (or neutralization) titrations, 414; Precipitation titrations, 415; Redox titrations, 416; Complex-formation titrations
Null-Point Potentiometry
Dead-Stop End Point Potentiometry
Applications of Potentiometry and Potentiometric Titrations
Some Acid-Base and Redox Determinations
Determination of Ka of a weak acid, Determination of Fe(II) with KMnO4, Determination of the strength of K2Cr2O7 against Fe(II)

14. Conductometric Titrations
Introduction to Electrical Conductance
Specific conductance, Equivalent conductance, Relation between specific and equivalent conductances, Molar conductance
Variation of Molar Conductance with Dilution
Degree of Dissociation of a Weak Electrolyte
Kohlrausch's Law
Ostwald's Dilution Law
Conductivity Cells and Cell Constant
Conductivity Water
Platinization of Platinum Electrodes
Determination of Cell Constant
Measurement of the Conductivity Using Kohlrausch Wheatstone Bridge
Applications of Conductance Measurements
Determination of degree of dissociation, Ionic product of water, Solubilities and solubility products, Conductometric titrations
Conductometric Titrations, 441 Some typical titrations, strong acid-base titration, strong acid-weak base, weak acid-strong base, very weak acid with a strong base, weak acid-weak base, mixture of a strong and weak acids with a strong base, displacement (or replacement), Precipitation titrations, Advantages
Oscillometry (High Frequency Titrations)
Applications

15 Voltammetry and Polarographic Methods
Introduction
Excitation Signal
Voltammetric Cell
Polarography
Dropping mercury electrode (DME), merits, demerits, its handling (precautions), Experimental details, Procedure, Circuit of a simple manual polarograph, Miscellaneous phenomena at the DME
Current-Voltage Curve (Basis of Polarography)
Ilkovic Equation
Residual Currents
Half-Wave Potentials
Polarographic Maxima
Quantitiative Evaluation of a Polarographic Wave
Exact procedure, Approximate procedure, Graphical method
Polarographic Methods of Analysis
Direct comparison method, Internal standard (or pilot ion method), Standard addition method
Organic Polarographic Analysis
Applications of Polarography
Inorganic applications, Analysis of mixtures, Determination of stability constant of complexes, Organic applications
Comparison of Polarography and Amperometry

16 Amperometry
Introduction
Types of Amperometric Titration Curves
Volume Changes
Advantages of Amperometric Titrations
Disadvantages
Instrumentation
Amperometric titrations with DME, Lingane and Laitinen cells
Rotating Platinum Microelectrode
Applications of Amperometric Titrations Determination of Ni2+ with DMG (amperochelometry)
Successive determination of Cl–, Br– and I–
Biamperometric (Using Two Indicator Electrodes) Titrations
Water (Moisture) Determination by Amperometry

17 Coulometry
Introduction
Controlled-Potential Coulometry
Instrumentation, Applications
Amperostatic Coulometry (Coulometric Titrimetry)
Titration cell, 496; principles, 497; End point detection
Instrumentation
Advatnages of Coulometric Titrations
Errors in Coulometric Titrations
Applications
Neutralization titrations, Precipitation and complex formation titrations, Oxidation-reduction titrations
Coulometric Titration of Cyclohexene with Bromine

APPENDICES
I List of Analytical Abbreviations
II Symbols, Conversion Factors, and Prefixes
III Use of Logarithm
IV Molar Masses of Some Compounds
V pH Indicators
VI Density of Solutions
VII Solubility Product Constants
VIII Tables Related to Specific and Equivalent Conductances
IX Some Standard and Formal Reduction Electrode Potentials
X Common Chromophores : Electronic Absorption Characteristics
XI Characteristic Infrared Absorption Bands
XII Resonance Lines for Atomic Absorption
XIII Polarographic Half-Wave Potentials
XIV A Comparison of Trace Element Detection Limits by FES and FAAS
XIV-A Dissociation Constants of Some Acids in Water at 25°C
     -B Acidic Dissociation Constants of Some Bases in Water at 25°C