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Contents
Chapter 1 Analytical Objectives, or: What Analytical Chemists Do
1.1 What Is Analytical Science?
1.2 Qualitative and Quantitative Analysis: What Does Each Tell Us?
1.3 Getting Started: The Analytical Process
Defining the Problem——What do we Really Need to Know? (Not Necessarily Everything)
Obtaining a Representative Sample——We Can’t Analyze the Whole Thing
Preparing the Sample for Analysis——It Probably Needs to be Altered
Performing Necessary Chemical Separations
Performing the Measurement——You Decide the Method
Instrument Standardization
Method of Standard Additions
Internal Standard Calibration
Calculating the Results and Reporting the Data
1.4 Validation of a Method-You Have to Prove It Works!
1.5 Analyze Versus Determine-They Are Different
1.6 Some Useful Websites
Chapter 2 Basic Tools and Operations of Analytical Chemistry
2.1 The Laboratory Notebook-Your Critical Record
2.2 Laboratory Materials and Reagents
2.3 The Analytical Balance-The Indispensible Tool
Single-Pan Mechanical Balance
Semimicro-And Microbalances
Zero-Point Drift
Weight in a Vacuum——This is the Ultimate Accuracy
Sources of Error in Weighing
General Rules for Weighing
Weighing of Solids
Weighing of Liquids
Types of Weighing——What Accuracy do you Need?
2.4 Volumetric Glassware-Also Indispensible
Volumetric Flasks
Pipets
Syringe Pipets
Burets
Care and Use of Volumetric Glassware
General Tips for Accurate and Precise Titrating
Tolerances and Precision of Glassware
Calibration of Glassware——For the Ultimate Accuracy
Techniques for Calibrating Glassware
Selection of Glassware——How Accurate Does it have to be?
2.5 Preparation of Standard Base Solutions
2.6 Preparation of Standard Acid Solutions
2.7 Other Apparatus-Handling and Treating Samples
Blood Samplers
Desiccators
Furnaces and Ovens
Hoods
Wash Bottles
Centrifuges and Filters
Techniques of Filtration
2.8 Igniting Precipitates-Gravimetric Analysis
2.9 Obtaining the Sample-Is It Solid, Liquid, or Gas?
2.10 Operations of Drying and Preparing a Solution of the Analyte
Drying the Sample
Sample Dissolution
Dissolving Inorganic Solids
Destruction of Organic Materials for Inorganic Analysis——Burning or Acid Oxidation
Microwave Preparation of Samples
Partial Destruction or Nondestruction of Sample Matrix
Protein-Free Filtrates
Laboratory Techniques for Drying and Dissolving
2.11 Laboratory Safety
Chapter 3 Statistics and Data Handling in Analytical Chemistry
3.1 Accuracy and Precision: There Is a Difference
3.2 Determinate Errors-They Are Systematic
3.3 Indeterminate Errors-They Are Random
3.4 Significant Figures: How Many Numbers Do You Need?
Absolute and Relative Uncertainty
Propagation of Uncertainties
Addition and Subtraction——Think Absolute
Multiplication and Division——Think Relative
Putting it All Together
Logarithms——Think Mantissa
3.5 Rounding Off
3.6 Ways of Expressing Accuracy
Absolute Errors
Relative Error
3.7 Standard Deviation-The Most Important Statistic
3.8 Propagation of Errors-Not Just Additive
3.9 Significant Figures and Propagation of Error
3.10 Control Charts
3.11 The Confidence Limit-How Sure Are You?
3.12 Tests of Significance-Is There a Difference?
3.13 Rejection of a Result: The Q Test
3.14 Statistics for Small Data Sets
The Median may be Better than the Mean
Range Instead of the Standard Deviation
Confidence Limits Using the Range
3.15 Linear Least Squares-How to Plot the Right Straight Line
3.16 Correlation Coefficient and Coefficient of Determination
3.17 Detection Limits-There Is No Such Thing as Zero
3.18 Statistics of Sampling-How Many Samples, How Large?
3.19 Powering a Study: Power Analysis
3.20 Use of Spreadsheets in Analytical Chemistry
Filling the Cell Contents
Saving the Spreadsheet
Printing the Spreadsheet
Relative Vs. Absolute Cell References
Use of Excel Statistical Functions
Useful Syntaxes
Text Website Examples
3.21 Using Spreadsheets for Plotting Calibration Curves
3.22 Slope, Intercept, and Coefficient of Determination
3.23 LINEST for Additional Statistics
3.24 Statistics Software Packages
Chapter 4 Good Laboratory Practice: Quality Assurance and Method Validation
4.1 What Is Good Laboratory Practice?
4.2 Validation of Analytical Methods
4.3 Quality Assurance-Does the Method Still Work?
4.4 Laboratory Accreditation
4.5 Electronic Records and Electronic Signatures: 21 CFR, Part 11
Electronic Records
Electronic Signatures
Epa: Cromerr
4.6 Some Official Organizations
Chapter 5 Stoichiometric Calculations: The Workhorse of the Analyst
5.1 Review of the Fundamentals
The Basics: Atomic, Molecular, and Formula Weights
What is a Dalton?
Moles: The Basic Unit for Equating Things
5.2 How Do We Express Concentrations of Solutions?
Molarity——The Most Widely Used
Normality
Formality——Instead of Molarity
Molality——The Temperature-Independent Concentration
Density Calculations——How do we Convert to Molarity?
Analytical and Equilibrium Concentrations——They are not the Same
Dilutions——Preparing the Right Concentration
More Dilution Calculations
5.3 Expressions of Analytical Results-So Many Ways
Solid Samples
Liquid Samples
5.4 Volumetric Analysis: How Do We Make Stoichiometric Calculations?
Titration——What are the Requirements?
Standard Solutions——There are Different Kinds
Classification of Titration Methods——What Kinds are there?
5.5 Volumetric Calculations-Let's Use Molarity
Some Useful Things to know for Molarity Calculations
Standardization and Titration Calculations——They are the Reverse of one Another
What if the Analyte and Titrant can React in Different Ratios?
If the Reaction is Slow, do a Back-Titration
5.6 Titer-How to Make Rapid Routine Calculations
5.7 Weight Relationships-You Need These for Gravimetric Calculations
Chapter 6 General Concepts of Chemical Equilibrium
6.1 Chemical Reactions: The Rate Concept
6.2 Types of Equilibria
6.3 Gibbs Free Energy and the Equilibrium Constant
6.4 Le Cha^telier's Principle
6.5 Temperature Effects on Equilibrium Constants
6.6 Pressure Effects on Equilibria
6.7 Concentration Effects on Equilibria
6.8 Catalysts
6.9 Completeness of Reactions
6.10 Equilibrium Constants for Dissociating or Combining Species-Weak Electrolytes and Precipitates
6.11 Calculations Using Equilibrium Constants-Composition at Equilibrium?
Chemical Reactions
Excel Goal Seek for Iterative Problem Solving
Using Goal Seek to Solve an Equation
Dissociation Equilibria
Shortcomings of Excel-Based Approaches and how to get around them
6.12 The Common Ion Effect-Shifting the Equilibrium
6.13 Systematic Approach to Equilibrium Calculations-How to Solve Any Equilibrium Problem
6.14 Some Hints for Applying the Systematic Approach for Equilibrium Calculations
6.15 Heterogeneous Equilibria-Solids Don't Count
6.16 Activity and Activity Coefficients-Concentration Is Not the Whole Story
6.17 The Diverse Ion Effect: The Thermodynamic Equilibrium Constant and Activity Coefficients
Chapter 7 Acid-Base Equilibria
7.1 The Early History of Acid-BaseConcepts
7.2 Acid-Base Theories-Not All Are Created Equal
Arrhenius Theory——H+ and oh−
Theory of Solvent Systems——Solvent Cations and Anions
Brønsted—Lowry Theory——Taking and Giving Protons
Lewis Theory——Taking and Giving Electrons
7.3 Acid-Base Equilibria in Water
7.4 The pH Scale
7.5 pH at Elevated Temperatures: Blood pH
7.6 Weak Acids and Bases-What Is the pH?
7.7 Salts of Weak Acids and Bases-They Aren't Neutral
7.8 Buffers-Keeping the pH Constant (or Nearly So)
7.9 Polyprotic Acids and Their Salts
7.10 Ladder Diagrams
7.11 Fractions of Dissociating Species at a Given pH: α Values-How Much of Each Species?
7.12 Salts of Polyprotic Acids-Acid, Base, or Both?
7.13 Physiological Buffers-They Keep You Alive
7.14 Buffers for Biological and Clinical Measurements
7.15 Diverse Ion Effect on Acids and Bases: cKa and cKb-Salts Change the pH
7.16 log C- pH Diagrams
7.17 Exact pH Calculators
Chapter 8 Acid-Base Titrations
8.1 Strong Acid versus Strong Base-The Easy Titrations
8.2 The Charge Balance Method-An Excel Exercise for the Titration of a Strong Acid and a Strong Base
8.3 Detection of the End Point: Indicators
8.4 Standard Acid and Base Solutions
8.5 Weak Acid versus Strong Base-A Bit Less Straightforward
8.6 Weak Base versus Strong Acid
8.7 Titration of Sodium Carbonate-A Diprotic Base
8.8 Using a Spreadsheet to Perform the Sodium Carbonate-HCl Titration
8.9 Titration of Polyprotic Acids
8.10 Mixtures of Acids or Bases
8.11 Equivalence Points from Derivatives of a Titration Curve
8.12 Titration of Amino Acids-They Are Acids and Bases
8.13 Kjeldahl Analysis: Protein Determination
8.14 Titrations Without Measuring Volumes
Chapter 9 Complexometric Reactions and Titrations
9.1 Complexes and Formation Constants-How Stable Are Complexes?
9.2 Chelates: EDTA-The Ultimate Titrating Agent for Metals
The Chelon Effect——The more Complexing Groups, the Better
Edta Equilibria
Formation Constant
Effect of pH On Edta Equilibria——How Much is Present as Y4−?
Conditional Formation Constant——Use for a Fixed pH
9.3 Metal-EDTA Titration Curves
9.4 Detection of the End Point: Indicators-They Are Also Chelating Agents
9.5 Other Uses of Complexes
9.6 Cumulative Formation Constants β and Concentrations of Specific Species in Stepwise Formed Complexes
Recommended References
Chapter 10 Gravimetric Analysis and Precipitation Equilibria
10.1 How to Perform a Successful Gravimetric Analysis
What Steps are Needed?
First Prepare the Solution
Then do the Precipitation——But Under the Right Conditions
Digest the Precipitate to Make Larger and More Pure Crystals
Impurities in Precipitates
Washing and Filtering the Precipitates——Take Care or you may Lose Some
Drying or Igniting the Precipitate
10.2 Gravimetric Calculations-How Much Analyte Is There?
10.3 Examples of Gravimetric Analysis
10.4 Organic Precipitates
10.5 Precipitation Equilibria: The Solubility Product
10.6 Diverse Ion Effect on Solubility: Ksp and Activity Coefficients
Chapter 11 Precipitation Reactions and Titrations
11.1 Effect of Acidity on Solubility of Precipitates: Conditional Solubility Product
11.2 Mass Balance Approach for Multiple Equilibria
11.3 Effect of Complexation on Solubility: Conditional Solubility Product
11.4 Precipitation Titrations
Titration Curves——Calculating pX
Stepwise Precipitation Titrations
Detection of the end Point: Indicators
Titration of Sulfate with Barium
Chapter 12 Electrochemical Cells and Electrode Potentials
12.1 What Are Redox Reactions?
12.2 Electrochemical Cells-What Electroanalytical Chemists Use
Voltaic Cell and Spontaneous Reactions——What is the Cell Potential?
Half-Reactions——Giving and Accepting Electrons
Half-Reaction Potentials——They are Measured Relative to Each Other
What Substances React?
Which is the Anode? and Which is the Cathode?
12.3 Nernst Equation-Effects of Concentrations on Potentials
12.4 Formal Potential-Use It for Defined Nonstandard Solution Conditions
12.5 Limitations of Electrode Potentials
Chapter 13 Potentiometric Electrodes and Potentiometry
13.1 Metal Electrodes for Measuring the Metal Cation
13.2 Metal-Metal Salt Electrodes for Measuring the Salt Anion
13.3 Redox Electrodes-Inert Metals
13.4 Voltaic Cells without Liquid Junction-For Maximum Accuracy
13.5 Voltaic Cells with Liquid Junction-The Practical Kind
13.6 Reference Electrodes: The Saturated Calomel Electrode
13.7 Measurement of Potential
13.8 Determination of Concentrations from Potential Measurements
13.9 Residual Liquid-Junction Potential-It Should Be Minimized
13.10 Accuracy of Direct Potentiometric Measurements-Voltage Error versus Activity Error
13.11 Glass pH Electrode-Workhorse of Chemists
Principle of the Glass Electrode
Combination pH Electrodes——A Complete cell
What Determines the Glass Membrane Potential?
Alkaline Error
Acid Error
13.12 Standard Buffers-Reference for pH Measurements
13.13 Accuracy of pH Measurements
13.14 Using the pH Meter-How Does It Work?
13.15 pH Measurement of Blood-Temperature Is Important
13.16 pH Measurements in Nonaqueous Solvents
13.17 Ion-Selective Electrodes
Glass Membrane Electrodes
Solid-State Electrodes
Liquid—Liquid Electrodes
Plastic Membrane—Ionophore Electrodes
Mechanism of Membrane Response
Selectivity Coefficient
Experimental Methods for Determining Selectivity Coefficients
Measurement with Ion-Selective Electrodes
13.18 Chemical Analysis on Mars using Ion-Selective Electrodes
Chapter 14 Redox and Potentiometric Titrations
14.1 First: Balance the Reduction-Oxidation Reaction
14.2 Calculation of the Equilibrium Constant of a Reaction-Needed to Calculate Equivalence Point Potentials
14.3 Calculating Redox Titration Curves
14.4 Visual Detection of the End Point
Self-Indication
Starch Indicator
Redox Indicators
14.5 Titrations Involving Iodine: Iodimetry and Iodometry
14.6 Titrations with Other Oxidizing Agents
14.7 Titrations with Other Reducing Agents
14.8 Preparing the Solution-Getting the Analyte in the Right Oxidation State before Titration
14.9 Potentiometric Titrations (Indirect Potentiometry)
pH Titrations——Using pH Electrodes
Precipitation Titrations——Using Silver Electrodes
Redox Titrations——Using Platinum Electrodes
Ion-Selective Electrodes in Titrations——Measuring pM
Derivative Titrations
Gran’s Plots for End-Point Detection
Automatic Titrators
Chapter 15 Voltammetry and Electrochemical Sensors
15.1 Voltammetry
The Voltammetric Cell——An Electrolytic Cell
The Current—Voltage Curve——The Basis of Voltammetry
Stepwise Reduction or Oxidation
The Supporting Electrolyte——Needed for Voltammetric Measurements
Irreversible Reduction or Oxidation
The Working Potential Range——It Depends on the Electrode
15.2 Amperometric Electrodes-Measurement of Oxygen
15.3 Electrochemical Sensors: Chemically Modified Electrodes
15.4 Ultramicroelectrodes
15.5 Microfabricated Electrochemical Sensors
15.6 Micro and Ultramicroelectrode Arrays
Chapter 16 Spectrochemical Methods
16.1 Interaction of Electromagnetic Radiation with Matter
The Electromagnetic Spectrum
How Does Matter Absorb Radiation?
Rotational Transitions
Vibrational Transitions
Electronic Transitions
What Happens to the Absorbed Radiation?
16.2 Electronic Spectra and Molecular Structure
Kinds of Transitions
Absorption by Isolated Chromophores
Absorption by Conjugated Chromophores
Absorption by Aromatic Compounds
What if a Molecule Does not Absorb Radiation?
Inorganic Chelates: How do they Absorb so Intensely?
16.3 Infrared Absorption and Molecular Structure
16.4 Near-Infrared Spectrometry for Nondestructive Testing
Overtones and Bands——The Basis of Nir Absorption
Short- And Long-Wavelength Nir
Nir for Nondestructive Testing——How do we Calibrate?
Some Uses of Nir Spectrometry
16.5 Spectral Databases-IdentifyingUnknowns
16.6 Solvents for Spectrometry
16.7 Quantitative Calculations
Beer’s Law——Relating the Amount of Radiation Absorbed to Concentration
Mixtures of Absorbing Species
General Solution to the Determination of two Components in a Mixture
Quantitative Measurements from Infrared Spectra
16.8 Spectrometric Instrumentation
Sources
Monochromators
Sample Cells
Optical Fibers and Liquid Core Waveguide Cells
Detectors
Slit Width——Physical Vs. Spectral
Instrumental Wavelength and Absorbance Calibration
16.9 Types of Instruments
16.10 Array Spectrometers-Getting the Entire Spectrum at Once
16.11 Fourier Transform Infrared Spectrometers
16.12 Near-IR Instruments
16.13 Spectrometric Error in Measurements
16.14 Deviation from Beer's Law
Chemical Deviations
Instrumental Deviations
16.15 Fluorometry
Principles of Fluorescence
Chemical Structure and Fluorescence
Fluorescence Quenching
Relationship Between Concentration and Fluorescence Intensity
Fluorescence Instrumentation
Fluorescence Lifetime and Gated Fluorescence/Phosphorescence Measurement
Fluorescence Vs. Absorbance
16.16 Chemiluminescence
16.17 Fiber-Optic Sensors
Chapter 17 Atomic Spectrometric Methods
17.1 Principles: Distribution between Ground and Excited States-Most Atoms Are in the Ground State
17.2 Flame Emission Spectrometry
17.3 Atomic Absorption Spectrometry
17.4 Sample Preparation-Sometimes Minimal
17.5 Internal Standard and Standard Addition Calibration
17.6 Atomic Emission Spectrometry: The Induction Coupled Plasma (ICP)
17.7 Atomic Fluorescence Spectrometry
Chapter 18 Sample Preparation: Solvent and Solid-Phase Extraction
18.1 Distribution Coefficient
18.2 Distribution Ratio
18.3 Percent Extracted
18.4 Solvent Extraction of Metals
Extraction of Ion-Association Complexes
Extraction of Metal Chelates
Extraction Process for Metal Chelates
18.5 Accelerated and Microwave-Assisted Extraction
18.6 Solid-Phase Extraction
18.7 Microextraction
18.8 Solid-Phase Nanoextraction (SPNE)
Chapter 19 Chromatography: Principles and Theory
19.1 Countercurrent Extraction: The Predecessor to Modern Liquid Chromatography
19.2 Principles of Chromatographic Separations
19.3 Classification of Chromatographic Techniques
19.4 Theory of Column Efficiency in Chromatography
Theoretical Plates
Rate Theory of Chromatography——The Van Deemter Equation
Reduced Plate Height
Open Tubular Columns
High-Performance Liquid Chromatography: The Huber and Knox Equations
Efficiency and Particle Size in HPLC
Retention Factor Efficiency and Resolution
Resolution in Chromatography
19.5 Chromatography Simulation Software
Chapter 20 Gas Chromatography
20.1 Performing GC Separations
20.2 Gas Chromatography Columns
Packed Columns
Capillary Columns——The Most Widely Used
Stationary Phases——The key to Different Separations
Retention Indices for Liquid Stationary Phases
Analyte Volatility
20.3 Gas Chromatography Detectors
20.4 Temperature Selection
20.5 Quantitative Measurements
20.6 Headspace Analysis
20.7 Thermal Desorption
20.8 Purging and Trapping
20.9 Small and Fast
20.10 Separation of Chiral Compounds
20.11 Two-Dimensional GC
Chapter 21 Liquid Chromatography and Electrophoresis
21.1 High-Performance Liquid Chromatography
Principles
HPLC Subclasses
21.2 Stationary Phases in HPLC
21.3 Equipment for HPLC
21.4 Ion Chromatography
21.5 HPLC Method Development
21.6 UHPLC and Fast LC
21.7 Open Tubular Liquid Chromatography (OTLC)
21.8 Thin-Layer Chromatography
Stationary Phases for TLC/HPTLC
Mobile Phases for TLC
Sample Application
Developing the Chromatogram
Visualization. Detection of the Spots
Quantitative Measurements
21.9 Electrophoresis
21.10 Capillary Electrophoresis
Operation
Detectors in CE
How CE can Provide Highly Efficient Separations
Electrophoretic Mobility and Separation
Plate Numbers and Resolution in CE
21.11 Electrophoresis Related Techniques
Separation of Neutral Molecules: MEKC
Capillary Electrochromatography
Isotachophoresis and Capillary Isotachophoresis
Chapter 22 Mass Spectrometry
22.1 Principles of Mass Spectrometry
22.2 Inlets and Ionization Sources
22.3 Gas Chromatography-Mass Spectrometry
22.4 Liquid Chromatography-Mass Spectrometry
22.5 Laser Desorption/Ionization
22.6 Secondary Ion Mass Spectrometry
22.7 Inductively Coupled Plasma-Mass Spectrometry
22.8 Mass Analyzers and Detectors
Quadrupole Mass Filter
Ion Trap
Time-of-Flight
Ion Cyclotron Resonance
Ion Detectors
22.9 Hybrid Instruments and Tandem Mass Spectrometry
Chapter 23 Kinetic Methods of Analysis
23.1 Kinetics-The Basics
First-Order Reactions
Second-Order Reactions
Reaction Time
23.2 Catalysis
23.3 Enzyme Catalysis
Enzyme Kinetics
Properties of Enzymes
Enzyme Inhibitors and Activators
The Michaelis Constant
Enzyme Specificity
Enzyme Nomenclature
Determination of Enzymes
Determination of Enzyme Substrates
Example Enzymatic Analyses
Chapter 24 Automation in Measurements
24.1 Principles of Automation
24.2 Automated Instruments: Process Control
24.3 Automatic Instruments
24.4 Flow Injection Analysis
24.5 Sequential Injection Analysis
24.6 Laboratory Information Management Systems
Appendix A Literature of Analytical Chemistry
A.1 Journals
A.2 General References
A.3 Inorganic Substances
A.4 Organic Substances
A.5 Biological and Clinical Substances
A.6 Gases
A.7 Water and Air Pollutants
A.8 Occupational Health and Safety
Appendix B Review of Mathematical Operations: Exponents, Logarithms, and the Quadratic Formula
B.1 Exponents
B.2 Taking Logarithms of Numbers
B.3 Finding Numbers from Their Logarithms
B.4 Finding Roots with Logarithms
B.5 The Quadratic Formula
Appendix C Tables of Constants
Appendix F Answers to Problems
Index