Instrumental Analysis

"CHAPTER 1 - The Analyst's Toolbox Profile - A Scenario 1.2 - Introduction 1.2 - Ultraviolet - visible Spectroscopy 1.3 - Infrared Spectroscopy Compare and Contrast - UV-vis vs. FTIR in Quantitative Analysis 1.4 - Nuclear Magnetic Resonance Spectrometry 1.5 - Mass Spectrometry Profile - Putting it All Together 1.6 - Chromatography Profile - Establishing a Forensic Protocol 1.7 - Further Reading 1.8 - Additional Exercises CHAPTER 2 - Quantum Mechanics and Spectroscopy Profile- The Brain Initiative and everyday spectroscopy 2.1- Introduction 2.2- The interaction between electromagnetic radiation and matter - absorption and emission of light Profile - Erwin Schrödinger 2.3- Molecular vibrations lead to quantized energy levels Profile - London's Millennium Bridge Profile- Mass Dampers 2.4- Molecular rotation leads to quantized energy levels 2.5- Transitions between vibrational and rotational states -the role of thermal energy and nonradiative decay Prelude - The Boltzmann Distribution 2.6- Transitions between electronic, vibrational, and rotational states - putting it all together The Jablonski diagram Fluorescence and Phosphorescence 2.7 Energy levels of a proton in a magnetic field - Nuclear Magnetic Resonance (NMR) Spectroscopy 2.8- Additional Exercises CHAPTER 3 - An Introduction to Optics Profile: The diffraction grating is a key component for many optical instruments 3.1 - An Introduction to the Properties of Light Wavelength, Energy, and Frequency Coherence Polarization Interference Diffraction Scattering Profile- The photoelectric effect shows the particle nature of light 3.2- Controlling optical beams Mirrors and Reflection Lenses and Refraction Collecting and Collimating Light Focusing a Collimated Laser Beam Polarizers 3.3- Wavelength Selection Introduction to Prism and Grating Monochromators The Diffraction Grating Putting it all together- Details on the Grating Monochromator Profile- Optics that operate by diffraction- the Fresnel Zone Plate The Michelson Interferometer Optical Filters & Power Reduction 3.4 - Common Optical Materials 3.5- Beyond Linear Optics Profile- Innovation and discovery in optics - metamaterials hold promise for the perfect lens, invisibility cloaks, and more 3.6- Further Reading 3.7 - Additional Exercises CHAPTER 4 - An Introduction to Instrumental Electronics 4.1 - Introduction Circuit Symbols 4.2 - DC Circuits Current, Voltage, and Multimeter Basics Series Circuit Elements and the Voltage Divider Parallel Circuit Elements and the Current Divider The Multimeter Voltage and Current Loading Error Profile - Electronics for a Very Simple Light Sensing Instrument: Voltage Divider Photoresistor circuit 4.3- Capacitors and RC Circuits 4.4- AC Circuits Ohm's law for AC circuits Low-pass, High-pass, Band-pass, and Band Stop Filters Activity- RC Filter Spreadsheet Tool 4.5 - Operational Amplifiers Inverting and Non-inverting op amps Summing op amp Current to Voltage Amplifier The Voltage Follower Op Amp Comparator Cascading op amps A Cascaded Op Amp Example- Instrumentation Op Amp Profile- Electronics for an Automatic Titrator: Cascaded Op Amps and the Differentiating Op Amp 4.6 - Quick Survey of Components Potentiometers Diode Transistors Profile- Electronics for a Simple Absorption Spectrophotometer: Op Amp Circuit as Current to Voltage Amplifier Profile- What if you need a constant voltage under varying loads? A basic schematic of a potentiostat 4.7 - Analog and Digital Signals 4.8 - Further Reading 4.9 - Additional Exercises CHAPTER 5 - Signals and Noise: An Introduction to Signal Processing Profile- Spectroscopy of single molecules? 5.1 - Introduction to Signals 5.2 - Sources and Characteristics of Noise 5.3 - Signal to Noise Ratio and Ensemble Averaging 5.4- Processing Signals with Hardware and Software Analog Filters Boxcar averaging with hardware Modulating Signals and the Lock-In Amplifier Digital Filters Rolling average, Boxcar average, Savitzky-Golay Filter, and Fourier Filtering 5.5 - Sampling Rates, the Nyquist Frequency, and Aliasing 5.6- Analog to Digital Conversion 5.7- Further Reading 5.8 - Additional Exercises CHAPTER 6 - Molecular Ultraviolet and Visible Spectroscopy. Profile - James Clerk Maxwell 6.1 - Introduction 6.2 - Electronic Excitation and Molecular Structure Structure and ""Color"" Heteroatoms DPK - A Case Study Solvent Polarity Transition Metal Coordination Compounds Vibronic Transitions Sidebar - The Spectroscopic Series 6.3 - Quantitative Measurements Selection Rules Beer's Law Sidebar - Derivation of Beer's Law Deviations from Beer's Law Bandwidth Resolution Activity - Explore the effects on the relationship of A vs. c 6.4 - Instrumentation Designs Fixed Wavelength Spectrometers Profile - HACH DR3900 Scanning Spectrometers Compare and Constrast - Single & Dual Beam Spectrometers Array Spectrophotometers 6.5 - Monochromators 6.6 - Sources Deuterium Arc/Tungsten Halogen Bulb Xenon Arc Lamps Light Emitting Diodes Profile - The Jaz® by Ocean Optics 6.7 - Detectors The PMT Photovoltaic Cells Charge Coupled Device 6.8 - Noise Stray Light Detector Noise Profile - Walter Hermann Schottky Source Noise 6.9 - Kinetic UV-vis Techniques Stop Flow UV-vis Flash Photolysis Profile - Building a functional monochromator 6.10 - Useful Data 6.11 - Further Reading 6.12 - Additional Exercises CHAPTER 7 - Atomic Absorption Spectroscopy 7.1- Introduction Profile - The Birth of Atomic Absorption Spectroscopy (AAS) 7.2 - Molecular vs. Atomic Absorption Analytical Specificity 7.3 - Spectral Bandwidth Lifetime Broadening Profile - Review of Term Symbols Magnetic Field Broadening Profile - Lightning over Salty Waters Pressure Broadening Note - IUPAC nomenclature for pressure broadening. Doppler Broadening 7.4 -AAS Sources The Hollow-Cathode Lamp Profile - Nutritional Contents of Breast Milk Electrodeless Discharge Lamps Activity - Soil Analysis 7.5 - Sample Introduction Flame - AAS The Flame The Flame Height Electrothermal-AAS/GFAAS Flame vs Electrothermal AAS Profile- AAS Analysis of Oil Hydride - AAS Cold Vapor-AAS Compare and Contrast - Detection Limit Ranges 7.6 - Measuring Atomic Absorption Background Correction Zeeman Background Correction Smith-Hieftje background correction Spectral Interference Profile-Demystifying the Zeeman Effect 7.7 - Sample Preparation Acid Digestion 7.8 - Performing an AAS analysis 7.9 - Further Reading 7.10 - Additional Exercises CHAPTER 8 - Luminescence Spectroscopy 8.1 - Introduction 8.2 - Theory Principles of Fluorescence and Phosphorescence Profile - Is your $100 bill real? Find out with time-resolved fluorescence Relating fluorescence and molecular structure Profile - Fluorescence quenching helps with aerodynamics 8.3 -The Fluorescence Spectrometer Excitation sources Wavelength discrimination and instrument resolution Detectors Putting it all together- Walking through the luminescence system Excitation spectra Sample introduction Profile- Fluorescence pushes the limits of detection- single molecule detection and femtomolar concentrations 8.4- Challenges with Fluorescence Spectroscopy Detector response correction Source intensity correction Stray light contamination Challenges with high absorbance Photobleaching 8.5 -Additional Fluorescence based techniques Chemiluminescence Fluorescence polarization Resonance energy transfer spectroscopy Multiphoton excitation 8.6 -Further Reading 8.7 - Additional Exercises Profile - Using fluorescence to determine concentrations of DNA and RNA CHAPTER 9 - Atomic Emission Spectroscopy 9.1 - Introduction Profile - Get The Lead Out 9.2 - The Atomizer and the Excitation Source Profile - Columbia Inductively Coupled Plasma Torch Direct Current Plasma Source Profile - The Plasma Torch Microwave Induced Plasma Source Profile - Atmospheric MP-AES Profile - LIBS in Space Laser Ablation Profile- Visualizing a Plasma 9.3 - Sample Introduction Applications Sources AAS vs. AES Sample preparation and interferences Zeeman Background Correction 9.4 - Measuring Atomic Emission Compare and Contrast FAAS, GFAAS & ICP-AES 9.5 -Further Reading 9.6- Additional Exercises CHAPTER 10 -X-Ray Related Techniques Profile - A modern day gold rush. 10.1- Principles of X-ray Fluorescence (XRF) Profile-W. C. Röntgen XRF Transitions: Terminology Photoelectric Absorption Compare and Contrast - Optical Absorption vs.Photoelectric Absorption Absorption of X-rays 10.2- X-ray Sources Radioisotopes X-ray tubes Synchrotron Radiation Profile -Lost Inscriptions 10.3- X-ray Optics Profile -XRF Analysis of a 15th Painting Reflection Optics Diffraction Optics Profile - Lost Painting by Vincent van Gogh 10.4- Wavelength Dispersive Spectrometers Sequential and Simultaneous WDXRF Detectors 10.5- Energy Dispersive Spectrometers EDXRF Detectors 10.6- Direct Comparison: WDXRF & EDXRF Compare and Contrast- AAS, AES & XRF 10.7- Sample Introduction 10.8- Total Reflection XRF (TXRF) Profile - Christiaan Huygens Profile- Max Von Laue 10.9- X-ray Induced Photoelectron Spectroscopy & Auger Electron Spectroscopy Compare and Contrast: XRF, XPS & AES XPS AES Profile - Pierre Victor Auger XPS & AES Instrumentation 10.10- Single Crystal X-ray Diffractometry Scatter X-ray Diffraction Bragg's Law Profile- Henry and Lawrence Bragg The Lattice Obtaining A Crystal Structure The Diffractometer 10.10- Further Reading 10.11- Additional Exercises Advanced Exercises CHAPTER 11 -Infrared Spectroscopy 11.1 -Chemical Structure and Molecular Vibrations Profile - The Future of FTIR Wavenumbers Group Frequencies Normal Modes Vibrational Categories Profile - Olive Oil The Selection Rules and Molecular Symmetry Vibronic Coupling 11.2 - Time Domain vs. Frequency Domain Spectroscopy: The Fourier Transformation Activity: Creating a Beat Pattern Activity: Performing a Fourier Transform 11.3 -FTIR & Wavelength Discrimination The Michelson Interferometer Resolution Activity: Exploring Resolution 11.4 -Sources The Nernst Glower The Globar Coiled Wire Sources Solid State Sources 11.5 -Detectors Thermal Detectors Pyroelectric Detectors Profile- PZT Ceramics Photoconductive Detectors Profile- MCT Detectors Quantum Well Detectors 11.6 -Spectral Output Transmittance vs. Absorbance Quantitative Measurements and Deviations from Beer's Law 11.7- Developments; Two Dimensional Infrared Spectroscopy 11.8 - Sample Introduction Optical Materials Gasses Solution IR Spectroscopy Neat Liquids Solids ATR Compare and Contrast: UV-vis versus FTIR in Quantitative & Qualitative Analysis 11.9 - Useful Data 11.10 - Further Reading 11.11- Additional Exercises CHAPTER 12 - Raman Spectroscopy Profile - Raman Applications in Art and Medicine 12.1 -Introduction Rayleigh Scattering 12.2 - Theory of Raman Scattering Selection Rules Case Study - Vibrations in the linear molecule CO2 Case Study- Raman spectroscopy of a tetrahedral molecule; CCl4 12.3 -The Raman Spectrometer Instrument Basics Radiant Source Wavelength Discrimination and Raman Spectrometer Resolution Filters Detectors Compare and Contrast - A side-by-side evaluation of FTIR and Raman spectroscopy. Handheld Raman Analyzers Profile - Drug detection using commercial handheld Raman spectrometers Fiber optic probes 12.4- Additional Raman based techniques Raman Imaging Polarized Raman Spectroscopy Fourier Transform Raman Spectroscopy (FT-Raman) Surface enhanced Raman Spectroscopy (SERS) Profile - Using Raman spectroscopy to identify compounds from a distance 12.5 - Further Reading 12.6 - Additional Exercises CHAPTER 13 - Mass Spectrometry 13.1 - Basic Principles & Comparisons to an Optical Spectrophotometer Profile - Puffer MS 13.2 - Ion sources Electron Ionization Profile - J. J. Thomson Chemical Ionization Electrospray Ionization Profile - John Fenn Matrix Assisted Laser Desorption Ionization Secondary Ion Thermal Ionization Inductively Coupled Plasma Compare & Contrast - Elemental Methods Profile - TOF-MS in Space 13.3 - Mass Analyzers Sector & Double-focusing Profile - Eugen Goldstein Quadrupole Profile - R. Graham Cooks Time-of-flight FT Ion Cyclotron Resonance 13.4 - Detectors Activity - Selected Ion Game 13.5 - Additional Techniques Tandem Techniques Isotope Ratio Mass Spectrometry Accelerator Mass Spectrometry Profile - 10Be as a Geological Clock Profile - Human Scent Fingerprinting 13.6 - Further Reading 13.7 - Additional Exercises Advanced Exercises CHAPTER 14 - An Introduction to Nuclear Magnetic Resonance Spectroscopy 14.1 - Introduction Profile - NMR versus HIV Spectral Analysis - A Quick Review 14.2 - NMR Spectroscopy is all about the Nucleus Nuclear Quantum Numbers A Nucleus in a Magnetic Field Tesla vs. MHz 14.3 - The NMR Signal Compare and Contrast - Population distribution for common spectroscopic methods Profile - Felix Bloch 14.4 - The RF Pulse: Inducing nuclear magnetic resonance FT-NMR: Time Domain vs. Frequency Domain Spectroscopy & The Fourier Transformation Free Induction Decay (FID): The FT-NMR ""Beat Pattern"" 14.5 - Chemical Shift and Resolution Profile - Richard R. Ernst The Chemical Shift (ppm) Chemical Shift Reference Resolution 14.6 - The Instrument Shimming Loading 14.7 - Signal Processing Increasing the signal to noise ratio Profile - Angela Gronenborn 14.8 - Magnetic Resonance Imaging Profile - MRI and Brain Concussion 14.9 - Further Reading Texts On Line Resources Some interesting laboratory experiments 14.10 - Additional Exercises CHAPTER 15 - Liquid Chromatography 15.1 - Introduction Profile- Mikhail S. Tswett 15.2 - Theory Distribution Equilibrium Profile - Other Applications of Partition Coefficients Principles of Chromatography Activity: TLC at home The Retention Factor Resolution and Theoretical Plates Band Broadening 15.3 - Basic Method Development Thermodynamics and Kinetics Factors Isocratic vs. Gradient Profile: The Role of Temperature Qualitative vs. Quantitative Profile: Analysis of Wine - Qualitative and Quantitative 15.4 - Stationary Phase Materials and Modes of Separation Profile: LC-MS in Athletic Doping Normal Phase Reversed Phase Ion Exchange Hydrophilic Interaction Chromatography (HIC) Affinity Chiral Chromatography Profile - The Chiral Medicine Cabinet Size Exclusion 15.5 - Instrumentation Overview HPLC Components Profile -Ultrahigh Pressure LC Mobile Phase Columns Injectors Pumps Detectors Profile- Major Players, the Chromatography Industry 15.7 - Further Reading 15.8 - Additional Exercises CHAPTER 16 - Gas Chromatography Profile - Odorants, Pheromones, and Chemosignals 16.1 - Introduction Profile - Gas Chromatography on Mars 16.2 - Basic GC Instrument Design 16.3 - Method Development: a case study A Case Study - Peanut Butter Profile - The NIST 14 Gas Chromatography (GC) Library with Search Software 16.4 - Modes of Separation Isothermal vs. Temperature gradients The Column 16.5 - Carrier Gas and Injector Carrier Gases 16.6 - Detectors Ionizing Detectors Optical Detectors Thermal Conductivity Detectors Electrochemical Detectors Tandem Instrument Detection Quantitative and Qualitative Considerations 16.7 - New Developments and Directions in GC Multidimensional GC Techniques Profile - Breath and Air Quality Miniaturization, Portability, Speed, and Throughput 16.8 - Extended Theory Evaluation of the GC Separation The Relationship between VN, k, and Selectivity The General Elution Problem 16.9 - Useful Information Table 16.3 - GC column Manufacturers 16.10 - Further Reading 16.11 - Additional Exercises CHAPTER 17 - Electrophoresis 17.1 - Introduction Profile - The Father of Electrophoresis 17.2 - Fundamental Principles 17.3 - The Basic Apparatus Profile - DNA Markers 17.4 - Paper Electrophoresis Activity -Demystifying Electrophoresis: Build Your Own Electrophoresis Apparatus 17.5 - Gel Electrophoresis Polyacrylamide Gel Electrophoresis (PAGE) SDS PAGE Agarose Gel Electrophoresis 17.6 - Ending the Analysis: The Time Factor 17.7 - Gel Sample Detection Visualization Blotting Quantitative Electrophoresis 17.8 - Enhancing Resolution Disc Electrophoresis Isoelectric Focusing 2D Gel Electrophoresis Techniques Profile - 2D Success 17.9 - Capillary Electrophoresis Profile - Capillary Electrophoresis and the Human Genome Project Introduction to Capillary Electrophoresis The Instrument Separation Efficiency Electroosmotic Flow Sample Loading and Throughput Dynamic Coating Detection Recent Developments in CE Compare and Contrast: A look back at four different separation techniques 17.10 - Useful Data Table 17.1 - Polyacrylamide Gel Separation Ranges Table 17.2 - Stains for Gels 17.11 - Further Reading 17.12 - Additional Exercises CHAPTER 18 - Potentiometry & Probes 18.1 -Basic Principles: Probes and Biosensors Profile- Handheld water quality probe 18.2 - Potentiometric Probes Profile - The Standard Hydrogen Electrode The pH Probe Profile - Nano-scale pH probe for in-vivo use The Nitrate Probe Profile - Construction of a Salicylate ISE The Oxygen Probe 18.3 - Non-potentiometric probes The Dissolved Oxygen The Chloride Probe The Total Salinity Probe 18.4 - Probes for Measurements in the Human Body The Glucose Probe - a Biosensor Profile- The Number of Adults Treated for Diabetes Doubled in a Decade The Alcohol Fuel Cell Probe Profile - ""Smart"" Toilets 18.5 - Further Reading 18.6 - Additional Exercises CHAPTER 19 - Analytical Voltammetry Profile - Behind Frankenstein 19.1 - Basic Principles Profile -Parsing Method Names 19.2 - The Three-Cell Electrode Cell 19.3 - Chronoamperometry The Experiment Noise in CA and Related Methods Charging Current Mass Transport Controlling Mass Transport Profile - Chronoamperometric Nerve Gas Sensor The Cottrell Equation Profile - VX Probe 19.4 - Linear Sweep and Cyclic Voltammetry Profile - The International Space Station Electronic Tongue Background The Experiment Reversibility Quantitative Analysis with CV - The Randles-Sevcik Equation Qualitative Analysis with CV Solvents, Electrolytes and the Electrochemical Window 19.5 - Square Wave Voltammetry 19.6 - Working Electrodes Common Working Electrodes Ultramicroelectrodes and Nanoelectrodes Profile - Cyclic Voltammetry in a Single Cell 19.7 - Useful Data Temperature Dependence of Reference Electrodes Temperature Dependence of Solvent Drying Techniques 19.8 - Further Reading 19.9 -Additional Exercises CHAPTER 20 - Material and Surface Analysis Techniques 20.1- Introduction Profile - Characterizing metal nanoparticles for water purification: electron microscopy in action 20.2- Microscopy Profile - Microscopy and the Nobel Prize in Physics Atomic Force Microscopy (AFM) Profile - Controlling the shape of silver nanoparticles with pH- AFM in action Scanning Tunneling Microscopy (STM) Transmission Electron Microscopy (TEM) and Scanning Electron Microscopy (SEM) Compare and Contrast - Resolutions for different microscopy techniques 20.3: Thermoanalytic Techniques Profile-Thermogravimetric Analysis Differential Thermal Analysis (DTA) Thermogravimetric Analysis (TGA) Profile- TG/MS Differential scanning calorimetry (DSC) Compare and Contrast: DTA, TGA, & DSC Profile - A Crime Scene Analysis 20.4 - Mechanical Stress Analysis Dynamic Mechanical Analysis 20.5- Further reading 20.6- Additional Exercises CHAPTER 21 - Advanced Topics in NMR: Understanding the NMR Experiment 21.1 - Introduction Profile - Adriaan ""Ad"" Bax 21.2 - Resonance in the Rotating Frame 21.3 - The Pulse Experiment Relaxation of the excited state Longitudinal Relaxation (Spin-Lattice): T1 Measuring T1: Inversion Recovery Transverse Relaxation (Spin-Spin): T2 Measuring T2: Spin-Echo 21.4 - The Influence of Nuclear Neighbors: J-Coupling Dipolar Coupling and The Nuclear Overhauser Effect Profile- Albert W. Overhauser Profile - Jean Jeener 21.5 - Introduction to 2D NMR COSY and TOSCY NOESY Profile - G. Marius Clore Profile - Kurt Wuthrich 21.6 - Special Topics in NMR Variable Temperature NMR Solid State NMR Other Spin-Active Nuclei Phosphorus-31 Nitrogen-15 Platinum-195 Fluorine-19 21.7 - Useful Data 21.8 - Further Reading 21.9 - Additional Exercises CHAPTER 22: Statistical Data Analysis 22.1-Introduction 22.2 -Types of Error Gross Error Systematic Error Random Error 22.3 -Precision vs. Accuracy 22.4 -Statistical Tools Population vs. Sample Mean Standard Deviation and Variance Standard Error and Error Bars. Normal Distributions Confidence Limits Using Spreadsheets to Determine Confidence Limits Propagation of Error Data Sets Identifying Outliers: The Q-Test Identifying Outliers: The Grubb's Test Analyzing Variance: The F-Test ANOVA: A 2-Dimenstional F-Test 22.5 -Linear Regression Analysis 22.6 -LOD, LOQ, and LDR 22.7 -Further Reading 22.8 - Additional Exercises Appendix: Table of Acronyms and Abreviations Index"